Processing biomass

ABSTRACT

Methods and systems are described for processing cellulosic and lignocellulosic materials into useful intermediates and products, such as energy and fuels. For example, conveying systems and methods, such as highly efficient vibratory conveyors, are described for the processing of the cellulosic and lignocellulosic materials.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.16/177,669, filed Nov. 1, 2018, which is a continuation of U.S.application Ser. No. 15/384,126, filed Dec. 19, 2016, now abandoned,which is a continuation of U.S. application Ser. No. 14/242,221, filedApr. 1, 2014, now U.S. Pat. No. 9,556,496, issued on Jan. 31, 2017,which is a continuation of PCT/US13/64289 filed Oct. 10, 2013, whichclaims priority to the following provisional applications: U.S. Ser. No.61/711,807, filed Oct. 10, 2012; U.S. Ser. No. 61/711,801, filed Oct.10, 2012; U.S. Ser. No. 61/774,684, filed Mar. 8, 2013; U.S. Ser. No.61/774,773, filed Mar. 8, 2013; U.S. Ser. No. 61/774,731, filed Mar. 8,2013; U.S. Ser. No. 61/774,735, filed Mar. 8, 2013; U.S. Ser. No.61/774,740, filed Mar. 8, 2013; U.S. Ser. No. 61/774,744, filed Mar. 8,2013; U.S. Ser. No. 61/774,746, filed Mar. 8, 2013; U.S. Ser. No.61/774,750, filed Mar. 8, 2013; U.S. Ser. No. 61/774,752, filed Mar. 8,2013; U.S. Ser. No. 61/774,754, filed Mar. 8, 2013; U.S. Ser. No.61/774,775, filed Mar. 8, 2013; U.S. Ser. No. 61/774,780, filed Mar. 8,2013; U.S. Ser. No. 61/774,761, filed Mar. 8, 2013; U.S. Ser. No.61/774,723, filed Mar. 8, 2013; and U.S. Ser. No. 61/793,336, filed Mar.15, 2013. The entire disclosure of each of these applications areincorporated by reference herein.

BACKGROUND

As demand for petroleum increases, so too does interest in renewablefeedstocks for manufacturing biofuels and biochemicals. The use oflignocellulosic biomass as a feedstock for such manufacturing processeshas been studied since the 1970s. Lignocellulosic biomass is attractivebecause it is abundant, renewable, domestically produced, and does notcompete with food industry uses.

Many potential lignocellulosic feedstocks are available today, includingagricultural residues, woody biomass, municipal waste, oilseeds/cakesand sea weeds, to name a few. At present these materials are either usedas animal feed, biocompost materials or are burned in a cogenerationfacility or are landfilled.

Lignocellulosic biomass comprises crystalline cellulose fibrils embeddedin a hemicellulose matrix, surrounded by lignin. This produces a compactmatrix that is difficult to access by enzymes and other chemical,biochemical and biological processes. Cellulosic biomass materials(e.g., biomass material from which the lignin has been removed) is moreaccessible to enzymes and other conversion processes, but even so,naturally-occurring cellulosic materials often have low yields (relativeto theoretical yields) when contacted with hydrolyzing enzymes.Lignocellulosic biomass is even more recalcitrant to enzyme attack.Furthermore, each type of lignocellulosic biomass has its own specificcomposition of cellulose, hemicellulose and lignin.

While a number of methods have been tried to extract structuralcarbohydrates from lignocellulosic biomass, they are either are tooexpensive, produce too low a yield, leave undesirable chemicals in theresulting product, or simply degrade the sugars.

Monosaccharides from renewable biomass sources could become the basis ofchemical and fuels industries by replacing, supplementing orsubstituting petroleum and other fossil feedstocks. However, techniquesneed to be developed that will make these monosaccharides available inlarge quantities and at acceptable purities and prices.

SUMMARY OF THE INVENTION

Disclosed are methods and systems for conveying carbohydrate containingmaterials prior to, during and/or after processing. In particular,methods for conveying the material using one or more vibratory conveyorsare disclosed.

Provided herein are methods of producing a treated biomass material,where the methods include: providing a starting biomass material;conveying the starting biomass material upon a vibratory conveyor; andexposing the starting biomass material to ionizing radiation while thebiomass is being conveyed upon the vibratory conveyer; thereby producinga treated biomass material. Optionally, the biomass defines asubstantially uniform thickness bed on the conveyor as it is beingexposed to the ionizing radiation. The method can further includedistributing the biomass material prior to conveying the biomassmaterial upon the vibratory conveyor and exposing the biomass toionizing radiation.

Also provided herein is an apparatus for producing a treated biomassmaterial, which includes: an ionizing radiation source; and a vibratoryconveying system, wherein the vibratory conveying system is capable ofconveying biomass past the ionizing radiation source.

The apparatus can also include an enclosure surrounding the biomass whenit is proximate to the radiation source. The enclosure can include awindow foil integrated into a wall of the enclosure, and wherein thewindow foil is disposed beneath the radiation source and allows passageof the electrons through the window foil and onto the biomass. Theapparatus and methods can further include a feeder conveying systemupstream from the vibratory conveying system, wherein the feederconveying system feeds the biomass to the vibratory conveying systemupstream of the radiation field. The feeder conveying system can also bea vibratory conveying system. One or both of the conveying systems canconvey the biomass at an average speed of 3 to 100 ft/min, at an averagespeed of 9 to 50 ft/min, or at an average speed of 10 to 25 ft/min.

The feeder conveying system can be used to distribute the biomassmaterial onto a bed of substantially uniform thickness. For example,seventy-five percent (75%) or more of the biomass material can be at theaverage bed thickness, or 80%, 85%, 90%, 95% or more of the biomassmaterial can be at the average bed thickness.

The biomass in the methods and apparatus can be comminuted prior tobeing exposed to the ionizing radiation. The type of comminution can beselected from the group consisting of: shearing, chopping, grinding,hammermilling or more than one of these. The comminution can produce astarting biomass material with particles, where greater than 80% or 85%of the particles have at least one dimension that is less than about0.25 inches, where greater than 90% of the particles have at least onedimension that is less than about 0.25 inches, or where greater than91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99% of the particles have atleast one dimension that is less than about 0.25 inches. The comminutioncan produce a starting biomass where no more than 5% of the particlesare less than 0.03 inches in their greatest dimension, where no morethan 5% of the particles are less than 0.02 inches in their greatestdimension or where no more than 5% of the particles are less than 0.01inches in their greatest dimension.

In the methods and apparatus, the source of the ionizing radiation canbe an electron beam, an ion beam, ultraviolet light with a wavelength ofbetween 100 nm and 280 nm, gamma radiation, X-ray radiation orcombinations thereof. An electron beam is preferred.

The biomass can be irradiated with 10 to 200 Mrad of radiation, with 10to 75 Mrad of radiation, with 10 to 15 Mrad of radiation, with 15 to 50Mrad of radiation or with 20 to 35 Mrad of radiation. The biomass can besubjected to multiple rounds of irradiation. For example, the biomasscan optionally be conveyed multiple times under a beam of ionizingradiation (e.g., 1, 2, 3, 4 or even more times). For, example, eachirradiation increasing total dosage of irradiation to the material withoptional cooling between irradiations.

The energy of the electron beam can be between 0.3 and 2 MeV, or between0.5 and 10 MeV, between 0.8 and 5 MeV, between 0.8 and 3 MeV, between 1and 3 MeV, and about 1 MeV.

In some implementations of the methods or apparatus the biomass materialis irradiated with an irradiating device with a power output of at least50 kW (e.g., at least 75 kW, at least 100, at least 125, at least 500kW).

In some implementation of the methods or systems, the biomass materialis conveyed at a rate of about 1000 to about 8000 lb/hr (e.g., betweenabout 2000 and 5000 lb/hr) using the vibratory conveyors. Optionally theconveyors can be made using structural materials that include steel suchas stainless steel (e.g., 304 or 316 L steel). Optionally the conveyorsinclude anti-stick coatings. For example, the conveyor can include atrough made of stainless steel.

In the methods and apparatus provided herein, the electron beam can besupplied by an electron accelerator equipped with a scanning horndisposed above the conveyor and configured to direct the electron beamonto the biomass upon the vibratory conveyor.

The biomass material can receive a substantially uniform level ofirradiation. The treated biomass material can exhibit a lower level ofrecalcitrance relative to the starting biomass material.

The starting biomass material can include a cellulosic orlignocellulosic material, such as wood, paper, paper products, cotton,grasses, grain residues, bagasse, jute, hemp, flax, bamboo, sisal,abaca, corn cobs, corn stover, coconut hair, algae, seaweed, straw,wheat straw or mixtures thereof.

In the methods and apparatus provided herein, at least a portion of theconveyor can include an enclosure.

A vibratory conveyor can provide an efficient mode of conveying biomassmaterial under an irradiation source. The oscillating motions in all thepossible combinations of x, y and z directions (where x is the directionof conveying, y is transverse to the direction of conveying, and z is inthe direction perpendicular to conveying and orthogonal to x and y) forexample, in the x direction, in x+z, and/or in x+y+z, provide manyadvantages while allowing conveying at a constant speed. The method andsystems described can also provide an efficient mode of spreading outbiomass material (for example, without additional spreading equipment orwith fewer burdens on the optional spreading equipment) to an eventhickness so that the irradiation can be substantially uniform. Afurther advantage over some other conveying systems and methods is thatthe biomass is turned and rotated, improving the irradiation uniformity,dosage averaging and cooling of the biomass. The uniform irradiation andimproved dosage averaging can provide a material that has reducedrecalcitrance throughout its bulk. Also, vibratory conveyors, forexample, in comparison to other conveying systems and methods, can belower in cost to operate. The methods and systems described herein canalso reduce the intensity of irradiation needed to irradiate through thebulk of a biomass and reduce costs and increase safety of used, e.g., byreducing the shielding that is required.

Implementations of the invention can optionally include one or more ofthe following summarized features. In some implementations, the selectedfeatures can be applied or utilized in any order while in othersimplementations a specific selected sequence is applied or utilized.Individual features can be applied or utilized more than once in anysequence. In addition, an entire sequence, or a portion of a sequence,of applied or utilized features can be applied or utilized once orrepeatedly in any order. In some optional implementations, the featurescan be applied or utilized with different, or where applicable the same,set or varied, quantitative or qualitative parameters as determined by aperson skilled in the art. For example, parameters of the features suchas size, individual dimensions (e.g., length, width, height), locationof, degree (e.g., to what extent such as the degree of recalcitrance),duration, frequency of use, density, concentration, intensity and speedcan be varied or set, where applicable as determined by a person ofskill in the art.

Features, for example, include: a method for exposing a biomass materialto ionizing radiation while the biomass material is being conveyed upona vibratory conveyor; the biomass material defines a substantiallyuniform thickness bed on the conveyor as it is being exposed to theionizing radiation; distributing the biomass material prior to conveyingthe biomass material upon the vibratory conveyer and exposing thebiomass to the ionizing radiation; distributing the biomass materialutilizes a feeder conveying system; the feeder conveying systemcomprises a second vibratory conveying system; seventy five percent ormore of the biomass material is distributed to be at the level of theaverage bed thickness; eighty five percent or more of the biomassmaterial is distributed to be at the level of the average bed thickness;ninety percent or more of the biomass material is distributed to be atthe level of the average bed thickness; ninety five percent or more ofthe biomass material is distributed to be at the level of the averagebed thickness; comminuting the biomass prior to exposing the biomass tothe ionizing radiation; comminuting consists of shearing; comminutingconsists chopping; comminuting consists of grinding; comminutingconsists of hammermilling; comminuting produces a biomass material withparticles; comminuting produces a biomass material wherein greater than80% of the particles have at least one dimension that is less than about0.25 inches; comminuting produces a biomass material wherein greaterthan 90% of the particles have at least one dimension that is less thanabout 0.25 inches; comminuting produces a biomass material whereingreater than 95% of the particles have at least one dimension that isless than about 0.25 inches; comminuting produces a biomass materialwherein no more than 5% of the particles are less than 0.03 inches intheir greatest dimension; the source of the ionizing is an electronbeam; the source of the ionizing is an ion beam; the source of theionizing is ultraviolet light with a wavelength of between 100 nm and280 nm; the source of the ionizing is gamma radiation; The source of theionizing is X-ray radiation; the biomass is irradiated with 10 to 200Mrad of radiation; the biomass is irradiated with 10 to 25 Mrad ofradiation; the biomass is irradiated with 10 to 75 Mrad of radiation;the biomass is irradiated with 15 to 50 Mrad of radiation; the biomassis irradiated with 20 to 35 Mrad of radiation; the energy of theelectron beam is between 0.3 and 2 MeV; the electron beam is supplied byan electron accelerator equipped with a scanning horn disposed above theconveyor and configured to direct the electron beam onto the biomassupon the vibratory conveyor; the biomass material receives asubstantially uniform level of ionizing radiation; the biomass materialcomprises a cellulosic or lignocellulosic material; The biomass materialincludes wood; The biomass material includes paper; the biomass materialincludes wood paper products; the biomass material includes cotton; thebiomass material includes grasses; the biomass material includes grainresidues; the biomass material includes bagasse; the biomass materialincludes jute; the biomass material includes hemp; the biomass materialincludes flax; the biomass material includes bamboo; the biomassmaterial includes sisal; the biomass material includes abaca; thebiomass material includes corn cobs; the biomass material includes cornstover; the biomass material includes coconut hair; the biomass materialincludes algae; the biomass material includes seaweed; the biomassmaterial includes straw; the biomass material includes wheat straw; atleast a portion of the conveyor comprises an enclosure; exposing thebiomass material to ionizing radiation reduces the recalcitrance of thebiomass material; the vibratory conveyer conveys the biomass material atan average speed of 3 to 100 ft/min; the vibratory conveyer conveys thebiomass material at an average speed of 9 to 50 ft/min; the vibratoryconveyer conveys the biomass material at an average speed of 12 to 25ft/min; the biomass material is irradiated with an irradiator with apower output of at least 50 kW; the biomass material is conveyed at arate of about 1000 to about 8000 lb/hr: the biomass is exposed toionizing radiation more than one time.

Some other features, for example, include: an apparatus for producing atreated biomass material including an ionizing radiation source and avibratory conveyor system, wherein the vibratory conveyor system iscapable of conveying biomass material past the ionizing radiationsource; an enclosure surrounding the biomass material when the biomassmaterial is proximate to a radiation source; the enclosure comprises awindow foil integrated into a wall of the enclosure, and wherein thewindow foil is disposed beneath the radiation source and allows passageof the electrons through the window foil and onto the biomass material;a feeder conveying system upstream from the vibratory conveying system,wherein the feeder conveying system is configured to spread the biomassmaterial to form a bed of biomass material of substantially uniformdepth, and where the feeder conveying system feeds the biomass materialto the vibratory conveying system upstream of the radiation field; thefeeder conveying system is a vibratory conveying system; the conveyorsystem comprises structural materials including steel.

Other features and advantages will be apparent from the followingdetailed description, and from the claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1A is a side view of a system for treating a biomass. FIG. 1B is atop view of a system for treating a biomass. FIG. 1C is a detailed viewof an irradiation zone. FIG. 1D is a right side view of a system fortreating a biomass. FIG. 1E is a front side detail view of a windowsystem of a system for treating biomass.

FIG. 2 is a flow diagram illustrating conversion of a biomass feedstockto one or more products.

FIG. 3A is a diagram illustrating, by exaggeration, the movement of aparticulate biomass on a first type of vibratory conveyor. FIG. 3B is adiagram illustrating, by exaggeration, the movement of a particulatebiomass on a second type of vibratory conveyor. FIG. 3C is a diagramillustrating, by exaggeration, the movement of a particulate biomass ona third type of vibratory conveyor.

FIG. 4 is a perspective view of a vibratory conveyor.

FIG. 5 is a perspective view of a vibratory conveyor with a cover.

FIG. 6A is a perspective view of a vibratory conveyor. FIG. 6B is a sideview of a vibratory conveyor.

FIG. 7 is a flow diagram showing a process for treating biomass.

DETAILED DESCRIPTION

Provided herein are methods and apparatus for producing a treatedbiomass material with a vibratory conveyer. The methods and apparatusprovide an advantage because the vibratory conveyor provides anefficient mode of conveying biomass material while it is under anirradiation source.

An exemplary embodiment is shown in FIGS. 1A-1E. FIG. 1A shows a frontside view of a system for irradiation of particulate biomass. Aspreader, for example, a distributer such as a CHRISTY SPREADER™ 110containing a biomass drops a controlled stream of biomass 112 onto thetrough of a covered vibratory conveyor 113 through an opening 114 in thecover of the conveyor. This aids in providing a substantially uniformthickness of the material spread across the conveyer. The coveredvibratory conveyor is supported by a support 184 and includes atransverse vibration system including leaf springs. The transverse driveassembly 186 provides horizontal oscillating movement to the trough. Thedrive motor includes an eccentric crank 198. The biomass is conveyed inthe direction of the shown arrows (downstream to upstream) through ascanning electron beam 116 generated by an electron beam irradiationdevice with an accelerating tube 118 and a scanning horn 120. Theelectron beam is extracted from the high vacuum side of the scan hornthrough a window foil, passes through an air gap, through a windowmounted in the cover 115, and irradiates the material 178 being conveyedbeneath. The irradiated material is then conveyed away from theirradiation area and drops into a collecting hopper 122. In preferredembodiments at least the irradiation zone (e.g., the region where theirradiation takes place) is in a vault, and optionally the entirevibratory conveyor and hoppers, for example, as outlined by the dottedline in FIG. 1A 192, can be in a vault. The biomass can enter viaingress 188 and egress 190 respectively.

In the embodiment above, as shown schematically as a top view of theconveyor surface by FIG. 1B, the area covered by the biomass below theopening of the hopper 124 is a small approximately rectangular areacompared to the width of the trough, its size being primarily determinedby the size and shape of the spreader opening and the vertical drop fromthe opening of the hopper to the trough surface. In some embodiments theopening width of the spreader is about the same as the width of theconveyor or it can be smaller than the width of the conveyor (e.g.,smaller than the conveyor by at least about 1%, smaller than theconveyor by at least about 5%, smaller than the conveyor by at leastabout 10%, smaller than the conveyor by at least about 15%, smaller thanthe conveyor by at least about 20%, smaller than the conveyor by atleast about 25%). As the biomass is conveyed in the direction indicatedby the arrows, the biomass is spread out over the entire width of thetrough so that at about the dashed line defined by AB and areasdownstream of this line, the biomass covers the entire width of thetrough. Additionally to this spreading, the biomass forms a layer ofsubstantially uniform thickness on the conveyor as the material movesdown the conveyor. At some distance from line AB, the electron beamimpinges on and through the biomass layer. The electron beam is rasterscanned over an area 126, the radiation area (zone, field, electronshower). A detailed view of the raster scan area is shown as FIG. 1C.The path of the raster (e.g., a locus of scanned electron beams) isshown projected on the surface of irradiated material wherein the arrowsshow the path of the raster scan. In other embodiments, the hopperopening is approximately commensurate in size with the trough so thatthe area 124 spans the entire width of the trough.

FIG. 1D shows a right side cut out view of a system for irradiatingbiomass. As shown, the biomass particles 178 form a uniform layer 150 asthey are conveyed through the electron beam 116 with minimal up and downmotion of the particles. The electron beam is extracted out of the highvacuum side of the scan horn 120 through the scan horn window 174 andthen through a window 115 mounted to the cover of the conveyor 113. Thetumbling and changing orientation of biomass particles, the evenspreading of the biomass along the whole width of the trough aspreviously discussed, and the raster scan of the e-beam ensures asubstantially uniform irradiation of the biomass as it moves down theconveyor through the electron beam shower. The movement of the biomasscan also help in cooling (e.g., air cooling) of the biomass.

FIG. 1E shows a cross sectional detailed view of the scan horn andwindow mounted in the cover. The scan horn includes horn window cooler170 and the conveyor includes enclosure window cooler 172 to blow air athigh velocity across the windows as indicted by the small arrows. Theelectrons in the electron beam 116 pass through the high vacuum of thescan horn 120 through the scan horn window 174, through the cooling airgap between the scan horn window and enclosure window, through theenclosure window 115 and impinge on and penetrate through the biomassmaterial 178 on the conveyor surface. The scan horn window is curvedtowards the vacuum side of the scan horn, for example, due to thevacuum. The enclosure window is shown curved towards the conveyedmaterial. The curvature of the windows can help the cooling air pathflow past the window for efficient cooling. The enclosure window ismounted on the cover 179 of the enclosed conveyor.

Biomass can be manufactured into various products by the methodsdescribed herein, for example, by reference to FIG. 2, showing a processfor manufacturing an alcohol can include, for example, optionallymechanically treating a feedstock 210. Such treatment can make thefeedstock easier to convey, for example, on with vibratory conveyorand/or pneumatic conveyor. Before and/or after this treatment, thefeedstock can be treated with another physical treatment, for example,irradiation while conveying on a vibratory conveyor as described herein,to reduce or further reduce its recalcitrance 212, and saccharifying thefeedstock, to form a sugar solution 214. Optionally, the method may alsoinclude transporting, e.g., by pipeline, railcar, truck or barge, thesolution (or the feedstock, enzyme and water, if saccharification isperformed en route) to a manufacturing plant 216. In some cases thesaccharified feedstock is further bioprocessed (e.g., fermented) toproduce a desired product 218 and byproduct 211. The resulting productmay in some implementations be processed further, e.g., by distillation220. If desired, the steps of measuring lignin content 222 and settingor adjusting process parameters based on this measurement 224 can beperformed at various stages of the process, as described in U.S. patentapplication Ser. No. 12/704,519, filed on Feb. 11, 2010, the entiredisclosure of which is incorporated herein by reference.

Vibratory conveyors work by the principle of applying an oscillatingforce or vibration to a material to be conveyed, and particularly to thetrough of a conveyor onto which the material to be conveyed is placed.The oscillating force can be supplied by a driver assembly that ismechanically coupled to the trough, as well as elastic elements alsomechanically coupled to the trough e.g., springs, leaf spring and/orcoil spring. The vibrations can be, for example, supplied by the driverassembly that can include one or more of the drive motors coupled to oneor more eccentric cranks or eccentric fly wheels. In some embodimentsthe vibratory conveyors are natural frequency vibrating conveyors basedon obtaining a common frequency between the elastic elements and thedrive assembly, for example, as disclosed in U.S. Pat. No. 4,813,532filed Jan. 15, 1988 and published Mar. 21, 1989, the entire disclosureof which is incorporated herein by reference.

The driver assembly, elastic elements and coupling to the trough canprovide motion to the surface of the trough, on which the feedstock tobe conveyed is placed. The motions include all combined directions andmagnitudes of x, y and z vectors, where x is the direction of conveyingbiomass, y is the direction transverse to conveying and z is thedirection perpendicular to and orthogonal to the x and y vectors. Thedisplacement distance of the trough can be varied for optimalperformance. For example, displacement in the x direction is betweenabout 1/16 inch and 12 inch (e.g., between about 1/16 inch and 8 inch,between about 1/16 inch and 4 inch, between about 1/16 inch and 1 inch,between about ⅛ inch and 12 inch, between about ⅛ inch and 6 inch,between about ⅛ inch and 2 inch, between about ⅛ inch and 1 inch,between about ¼ inch and 6 inch, between about ¼ inch and 4 inch,between about ¼ inch and 2 inch, between about ¼ inch and 1 inch,between about ½ inch and 6 inch, between about ½ inch and 4 inch,between about ½ inch and 2 inch, between about ½ inch and 1 inch,between about 1 inch and 6 inch, between about 1 inch and 4 inch).Displacement in the z direction can be, for example, be between about 0and 3 inch (e.g., between about 0.004 inch and 3 inch, between about0.008 inch and 3 inch, between about 0.016 inch and 3 inch, betweenabout 0.025 inch and 3 inch, between about 0.05 inch and 3 inch, betweenabout 0.1 inch and 3 inch, between about ¼ inch and 3 inch, betweenabout ½ inch and 3 inch, between about 1 inch and 3 inch, between about0.008 Inch and 1 inch, between about 0.016 inch and 1 inch, betweenabout 0.025 inch and 1 inch, between about 0.05 inch and 1 inch, betweenabout 0.1 inch and 1 inch, between about ¼ inch and 1 inch, betweenabout ½ inch and 1 inch, between about 1/16 inch and ¾ inch, betweenabout ⅛ inch and ¾ inch, between about ¼ inch and ¾ inch, between about½ inch and ¾ inch). For example, the displacement in the x direction canbe greater than the displacement in the z direction by a ratio less thanabout 3000:1 (e.g., less than about 1000 to 1, less than about 500 to 1,less than about 100 to 1, less than about 50 to 1, less than about 10 to1, less than about 5:1, less than about 2:1). The displacement in theydirection can be less than 1 inch (e.g., less than about 0.5 inch, lessthan about 0.1 inch, less than about 0.05 inch, less than about 0.005inch, or even about 0). The frequency of the oscillations can be between1 and 60 kHz. For example, the frequency can be between about 1 and 100Hz (e.g., between about 10 and 100 Hz, between about 20 and 100 Hz,between about 40 and 100 Hz, between about 60 and 100 Hz, between about10 and 80 Hz, between about 20 and 80 Hz, between about 40 and 80 Hz,between about 60 and 80 Hz, between about 20 and 60 Hz). The frequencyof oscillation can be higher. For example, the frequency of oscillationcan be between about 100 Hz and 20 kHz (e.g., between about 100 Hz and15 kHz, between about 100 Hz and 10 kHz, between about 100 Hz and 5 kHz,between about 500 Hz and 20 kHz, between about 500 Hz and 15 kHz,between about 500 Hz and 10 kHz, between about 500 Hz and 5 kHz, betweenabout 1 and 20 kHz, between about 1 and 15 kHz, between about 1 and 10kHz, between about 1 and 5 kHz). The frequency can be even much higher,for example, in the ultrasonic range (e.g., between about 20 and 60 kHz,between about 30 and 60 kHz, between about 40 and 60 kHz, between about50 and 60 kHz, between about 20 and 50 kHz, between about 30 and 50 kHz,between about 40 and 50 kHz, between about 20 and 40 kHz, between about30 and 40 kHz, between about 20 and 30 kHz).

There are at least three types of vibratory conveyors e.g., that can beutilized in the methods herein described. Combinations of these andalternatives can be designed. The three types of conveyors are discussedbelow.

In one type of vibratory conveyor, as depicted in FIG. 3A, a verticalforce is applied to the trough 310 and the trough is inclined at anangle α (alpha) to the horizontal, for example, at least 1° (arc degree)e.g., at least 5°, at least 10°, at least 20°). In another configurationthe trough is formed into a downwards series of steps (not shown) with adownward incline of at least 1° (e.g., at least 5°, at least 10°, atleast 20°, at least 30°, at least 40°, at least 50°, at least 60°). Amaterial, for example, shown as a particle 312 moves sequentially topositions, shown as open circles, the direction of movement shown byarrows. This movement occurs because an oscillatory force or vibrationalforce is applied perpendicular to the trough surface as shown by the twoheaded arrows. The oscillatory force repeatedly lofts the material to beconveyed perpendicular to the trough while gravity acts on the materialto move it down the incline, or alternatively the steps, of the trough.

In a second type of vibratory conveyor, depicted in FIG. 3B, thematerials to be conveyed are placed on a trough 320 and a purelyhorizontal force, indicated by the two headed arrow, causes a horizontalmovement of the materials. The force is an oscillating force such thatthe maximum horizontal vibratory forces applied to the trough in thedirection of conveyance is less than the static friction force actingbetween the trough and the material, while the forces applied to thematerial in the direction opposite to conveyance is higher than thestatic friction. In this way adherence is maintained between thematerial and the trough in the direction of conveyance but not in thedirection opposite conveyance and the material is conveyed forward in ashuffling manner. A material, for example, shown as particle 322 movessequentially to positions, shown as open circles, the shuffling movementindicated by the single headed arrows. As well as horizontal anddownwards conveying, these types of conveyors can convey materials inupwards direction of up to about 25 degrees.

In a third type of vibratory conveyor, depicted by FIG. 3C, the materialcarrying trough 330 is vibrated, as shown by the two headed arrows, atan angle β (beta) to the horizontal, for example, 45 degrees. Thematerial is lofted upwards and in the horizontal direction of incline.Therefore, the material is conveyed forward in a bouncing manner asdepicted by the particle 332 the movement indicated by the single headedarrows. As well as horizontal and downwards, these vibratory conveyorscan convey materials upwards as well as downwards, for example, at anupwards direction of up to about 25 degrees.

FIG. 4 is a perspective view of a vibratory conveyor of the third typedescribed above. The trough 410 has side walls 412 and 414 and issupported by support arms, legs or structures 416 that are pivotallyconnected to the trough on one end and pivotally connected to a basesupport 418 on the other end. Coil springs are 420 shown at a 45° to thetrough and support oscillations at this angle of the trough. A driveassembly 422 coupled to the trough provides the force for theoscillatory motion. Many other configurations of vibratory conveyors areknown. For example, instead of coil springs, leaf springs can be used.

FIG. 5 shows a perspective view of another example of a vibratoryconveyor of the third type. This example of a vibratory conveyorincludes a drive assembly 510, leaf springs 520, a trough 530, cover 540and access ports 550. Covers for the conveyors can be added to mitigate,for example, dust generation.

FIG. 6A shows a perspective view of a vibratory conveyor of the secondtype 610. The trough 612 carries biomass that has been delivered to theconveyor 630. At the upstream end of the conveyor where the biomass isdelivered, e.g., near 630, the biomass may form a pile with a peak.Downstream, e.g., near 640 the biomass is more uniformly spread. Thetrough is supported by support structures 616 which have pairs oflongitudinally spaced vertical legs 617, each pair of legs are connectedby horizontal cross members 618 and longitudinal base members 619. Thetrough 612 is suspended from the overhead structures 616 by verticalstraps 621. The straps 621 are attached at one end to the horizontalcross members 618 and at the other end to trough support members 622.The straps 621 are constructed of a dimension in the directiontransverse to the path of conveyance much larger than that of thedirection parallel to the path of conveyance, and therefore the verticalstraps 621 can act as resilient leaf-springs permitting displacement ofthe trough only in the direction of conveyance. The horizontaldeflection of the bottoms of the straps 621 combine with the forcesimparted by a vibration generating apparatus 623 creating motion of thetrough 612 in substantially horizontal direction with very littlevertical deflection. The vibration generating apparatus 623 can, forexample, include an eccentric fly wheels 683, 684, 685 and 686 as shownin front side view FIG. 6B. U.S. Pat. No. 5,131,525 (pub. Jul. 21, 1992)describes vibratory conveyors, the entire disclosure thereofincorporated herein by reference.

The vibratory conveyors described can include screens used for sievingand sorting materials. Port openings on the side or bottom of thetroughs can be used for sorting, selecting or removing specificmaterials, for example, by size or shape. Some conveyors havecounterbalances to reduce the dynamic forces on the support structure.Some vibratory conveyors are configured as spiral elevators, aredesigned to curve around surfaces and/or are designed to drop materialfrom one conveyor to another (e.g., in a step, cascade or as a series ofsteps or a stair). Along with conveying materials conveyors can be used,by themselves or coupled with other equipment or systems, for screening,separating, sorting, classifying, distributing, sizing, inspection,picking, metal removing, freezing, blending, mixing, orienting, heating,cooking, drying, dewatering, cleaning, washing, leaching, quenching,coating, de-dusting and/or feeding. The conveyors can also includecovers (e.g., dust-tight covers), side discharge gates, bottom dischargegates, special liners (e.g., anti-stick, stainless steel, rubber, customsteal, and or grooved), divided troughs, quench pools, screens,perforated plates, detectors (e.g., metal detectors), high temperaturedesigns, food grade designs, heaters, dryers and or coolers. Inaddition, the trough can be of various shapes, for example, flatbottomed, vee shaped bottom, flanged at the top, curved bottom, flatwith ridges in any direction, tubular, half pipe, covered or anycombinations of these. In particular, the conveyors can be coupled withan irradiation systems and/or equipment.

The conveyors (e.g., vibratory conveyor) can be made of corrosionresistant materials. The conveyors can utilize structural materials thatinclude stainless steel (e.g., 304, 316 stainless steel, HASTELLOY®ALLOYS and INCONEL® Alloys). For example, HASTELLOY® Corrosion-Resistantalloys from Hynes (Kokomo, Ind., USA) such as HASTELLOY® B-3® ALLOY,HASTELLOY® HYBRID-BC1® ALLOY, HASTELLOY® C-4 ALLOY, HASTELLOY® C-22®ALLOY, HASTELLOY® C-22HS® ALLOY, HASTELLOY® C-276 ALLOY, HASTELLOY®C-2000® ALLOY, HASTELLOY® G-30® ALLOY, HASTELLOY® G-35® ALLOY,HASTELLOY® N ALLOY and HASTELLOY® ULTIMET® alloy.

The vibratory conveyors can include non-stick release coatings, forexample, TUFFLON™ (DuPont, Delaware, USA). The vibratory conveyors canalso include corrosion resistant coatings. For example, coatings thatcan be supplied from Metal Coatings Corp (Houston, Tex., USA) and otherssuch as Fluoropolymer, XYLAN®, Molybdenum Disulfide, Epoxy Phenolic,Phosphate-ferrous metal coating, Polyurethane-high gloss topcoat forepoxy, inorganic zinc, Poly Tetrafluoro ethylene, PPS/RYTON®,fluorinated ethylene propylene, PVDF/DYKOR®, ECTFE/HALAR® and CeramicEpoxy Coating. The coatings can improve resistance to process gases(e.g., ozone), chemical corrosion, pitting corrosion, galling corrosionand oxidation.

In one embodiment, the conveyors include a cover. These enclosedconveyors are useful, for example, for the mitigation of dustgeneration. In some embodiments of these enclosed conveyors, a windowthat is transparent to the electron beam is mounted onto the cover, forexample, forming an integral part of the cover. The window can bealigned with the electron beam so that the electrons can pass throughthe window and irradiate material being conveyed through the radiationfield underneath the widow (e.g. underneath the electron beam). Thewindows are typically foils at least 10 um (micro meters) thick (e.g.,at least 15 um, at least 20 um, at least 25 um, at least 30 um, at least40 um). The electron beam generator also includes at least one windowfor extraction of electrons from the vacuum side of the generator to theatmospheric side. The distance between the facing surfaces of the windowfoil mounted to the electron beam generator (e.g., mounted to thescanning horn) and window foil mounted to the enclosure of the vibratoryconveyor, when the system is being used to irradiate a feedstock, is atleast about 0.1 cm (e.g. at least about 1 cm, at least about 2 cm, atleast about 4 cm, at least about 5 cm, at least about 6 cm, at leastabout 7 cm, at least about 8 cm, at least about 9 cm, or at least about10 cm, at least about 12 cm, at least about 15 cm). Preferably thewindow foils are cooled with a cooling fluid, for example, by using anair blower to blow air over the surface of the window foils.

It is generally preferred that the material be in a bed or layer ofsubstantially uniform thickness or depth while being irradiated. Forexample, a desired thickness can be, between about 0.0312 and 5 inches(e.g., between about 0.0625 and 2.000 inches, between about 0.125 and 1inches, between about 0.125 and 0.5 inches, between about 0.3 and 0.9inches, between about 0.2 and 0.5 inches between about 0.25 and 1.0inches, between about 0.25 and 0.5 inches, 0.100+/−0.025 inches,0.150+/−0.025 inches, 0.200+/−0.025 inches, 0.250+/−0.025 inches,0.300+/−0.025 inches, 0.350+/−0.025 inches, 0.400+/−0.025 inches,0.450+/−0.025 inches, 0.500+/−0.025 inches, 0.550+/−0.025 inches,0.600+/−0.025 inches, 0.700+/−0.025 inches, 0.750+/−0.025 inches,0.800+/−0.025 inches, 0.850+/−0.025 inches, 0.900+/−0.025 inches or0.900+/−0.025 inches.

Vibratory conveyors are particularly useful for spreading the materialand producing a uniform layer on the conveyor trough surface. Forexample, the initial feedstock can form a pile of material that can beat least four feet high (e.g., at least about 3 feet, at least about 2feet, at least about 1 foot, at least about 6 inches, at least about 5inches, at least about, 4 inches, at least about 3 inches, at leastabout 2 inches, at least about 1 inch, at least about ½ inch) and spansless than the width of the conveyor (e.g., less than about 10%, lessthan about 20%, less than about 30%, less than about 40%, less thanabout 50%, less than about 60%, less than about 70%, less than about80%, less than about 90%, less than about 95%, less than about 99%). Thevibratory conveyor can spread the material to span the entire width ofthe conveyor trough and have a uniform thickness, preferably asdiscussed above. In some cases, an additional spreading method can beuseful. For example, a spreader such as a broadcast spreader, a dropspreader (e.g., a CHRISTY SPREADER™) or combinations thereof can be usedto drop (e.g., place, pour, spill and/or sprinkle) the feedstock over awide area. Optionally, the spreader can deliver the biomass as a wideshower or curtain onto the vibratory conveyor. Additionally, a secondconveyor, upstream from the first conveyor (e.g., the first conveyor isused in the irradiation of the feedstock), can drop biomass onto thefirst conveyor, where the second conveyor can have a width transverse tothe direction of conveying smaller than the first conveyor. Inparticular, when the second conveyor is a vibratory conveyor, thefeedstock is spread by the action of the second and first conveyor. Insome optional embodiments, the second conveyor ends in a bias cross cutdischarge (e.g., a bias cut with a ratio of 4:1) so that the materialcan be dropped as a wide curtain (e.g., wider than the width of thesecond conveyor) onto the first conveyor. The initial drop area of thebiomass by the spreader (e.g., broadcast spreader, drop spreader,conveyor, or cross cut vibratory conveyor) can span the entire width ofthe first vibratory conveyor, or it can span part of this width. Oncedropped onto the conveyor, the material is spread even more uniformly bythe vibrations of the conveyor so that, preferably, the entire width ofthe conveyor is covered with a uniform layer of biomass. In someembodiments combinations of spreaders can be used. Some methods ofspreading a feed stock are described in U.S. Pat. No. 7,153,533, filedJul. 23, 2002 and published Dec. 26, 2006, the entire disclosure ofwhich is incorporated herein by reference.

Generally, it is preferred to convey the material as quickly as possiblethrough the electron beam to maximize throughput. For example, thematerial can be conveyed at rates of at least 1 ft/min, e.g., at least 2ft/min, at least 3 ft/min, at least 4 ft/min, at least 5 ft/min, atleast 10 ft/min, at least 15 ft/min, at least 20 ft/min, at least 25ft/min, at least 30 ft/min, at least 40 ft/min, at least 50 ft/min, atleast 60 ft/min, at least 70 ft/min, at least 80 ft/min, at least 90ft/min. The rate of conveying is related to the beam current andtargeted irradiation dose, for example, for a ¼ inch thick biomassspread over a 5.5 foot wide conveyor and 100 mA, the conveyor can moveat about 20 ft/min to provide a useful irradiation dosage (e.g. about 10Mrad for a single pass), at 50 mA the conveyor can move at about 10ft/min to provide approximately the same irradiation dosage.

The rate at which material can be conveyed depends on the shape and massof the material being conveyed. Flowing materials e.g., particulatematerials, are particularly amenable to conveying with vibratoryconveyors. Conveying speeds can, for example, be, at least 100 lb/hr(e.g., at least 500 lb/hr, at least 1000 lb/hr, at least 2000 lb/hr, atleast 3000 lb/hr, at least 4000 lb/hr, at least 5000 lb/hr, at least10,000 lb/hr, at least 15,000 lb/hr, or even at least 25,000 lb/hr).Some typical conveying speeds can be between about 1000 and 10,000lb/hr, (e.g., between about 1000 lb/hr and 8000 lb/hr, between about2000 and 7000 lb/hr, between about 2000 and 6000 lb/hr, between about2000 and 50001b/hr, between about 2000 and 4500 lb/hr, between about1500 and 5000 lb/hr, between about 3000 and 7000 lb/hr, between about3000 and 6000 lb/hr, between about 4000 and 6000 lb/hr and between about4000 and 5000 lb/hr). Typical conveying speeds depend on the density ofthe material. For example, for a biomass with a density of about 35lb/ft³, and a conveying speed of about 5000 lb/hr, the material isconveyed at a rate of about 143 ft³/hr, if the material is ¼″ thick andis in a trough 5.5 ft wide, the material is conveyed at a rate of about1250 ft/hr (about 21 ft/min). Rates of conveying the material cantherefore vary greatly. Preferably, for example, a ¼″ thick layer ofbiomass, is conveyed at speeds of between about 5 and 100 ft/min (e.g.between about 5 and 100 ft/min, between about 6 and 100 ft/min, betweenabout 7 and 100 ft/min, between about 8 and 100 ft/min, between about 9and 100 ft/min, between about 10 and 100 ft/min, between about 11 and100 ft/min, between about 12 and 100 ft/min, between about 13 and 100ft/min, between about 14 and 100 ft/min, between about 15 and 100ft/min, between about 20 and 100 ft/min, between about 30 and 100ft/min, between about 40 and 100 ft/min, between about 2 and 60 ft/min,between about 3 and 60 ft/min, between about 5 and 60 ft/min, betweenabout 6 and 60 ft/min, between about 7 and 60 ft/min, between about 8and 60 ft/min, between about 9 and 60 ft/min, between about 10 and 60ft/min, between about 15 and 60 ft/min, between about 20 and 60 ft/min,between about 30 and 60 ft/min, between about 40 and 60 ft/min, betweenabout 2 and 50 ft/min, between about 3 and 50 ft/min, between about 5and 50 ft/min, between about 6 and 50 ft/min, between about 7 and 50ft/min, between about 8 and 50 ft/min, between about 9 and 50 ft/min,between about 10 and 50 ft/min, between about 15 and 50 ft/min, betweenabout 20 and 50 ft/min, between about 30 and 50 ft/min, between about 40and 50 ft/min). It is preferable that the material be conveyed at aconstant rate, for example, to help maintain a constant irradiation ofthe material as it passes under the electron beam (e.g., shower, field).

FIG. 7 shows an irradiation process. This process can be part of theprocess described in FIG. 2 although it can alternatively be part of adifferent process. Initially, biomass can be delivered to a vibratoryconveyor 750. The biomass can be treated by a pre-irradiation process752 prior to it being conveyed through an irradiation zone 754. Afterirradiation, the biomass can be post processed 756. The process can berepeated (e.g., dashed arrow A).

Biomass can be delivered to the vibratory conveyor 750 by using anothervibratory conveyor, a belt conveyor, a pneumatic conveyor, a screwconveyor, a hopper, a dispersing machine (e.g., a spreader), a pipe,manually or by combination of these. The biomass can, for example, bedropped, poured, sprinkled and/or placed onto the vibratory conveyor byany of these methods. The biomass can be in a dry form, for example,with less than about 35% moisture content (e.g., less than about 20%,less than about 15%, less than about 10% or less about than 5%, lessthan about 4%, less than about 3%, less than about 2%, and even lessthan about 1%). The biomass can also be delivered in a wet state, forexample, as a wet solid, a slurry or a suspension with at least 10 wt %solids (e.g. at least 20 wt. %, at least 30 wt. %, at least 40 wt. %, atleast 50 wt. %, at least 60 wt. %, at least 70 wt. %).

In some cases, the pre-irradiation processing 752 includes screening ofthe biomass material. Screening can be by a vibratory screener coupledto the vibratory conveyor. For example, a vibratory screener that has amesh or perforated plate onto which the biomass falls with a desiredopening size, for example, less than 6.35 mm (¼ inch, 0.25 inch), {e.g.,less 3.18 mm (⅛ inch, 0.125 inch), less than 1.59 mm ( 1/16 inch, 0.0625inch), is less than 0.79 mm ( 1/32 inch, 0.03125 inch), e.g., less than0.51 mm ( 1/50 inch, 0.02000 inch), less than 0.40 mm ( 1/64 inch,0.015625 inch), less than 0.23 mm (0.009 inch), less than 0.20 mm (1/128 inch, 0.0078125 inch), less than 0.18 mm (0.007 inch), less than0.13 mm (0.005 inch), or even less than less than 0.10 mm ( 1/256 inch,0.00390625 inch)}. In one configuration the desired biomass fallsthrough the perforations or screen and thus biomass larger than theperforations or screen are not irradiated. These larger materials can bere-processed, for example, by comminuting, or they can simply be removedfrom processing. In another configuration material that is larger thanthe perforations is irradiated and the smaller material is removed bythe screening process or recycled by some other means. In this kind of aconfiguration, the conveyor itself (for example, a part of the conveyor)can be perforated or made with a mesh. For example, in a one particularembodiment the biomass material may be wet and the perforations or meshallow water to drain away from the biomass before irradiation.

Screening of material can also be by a manual method, for example, by anoperator or mechanoid (e.g., a robot equipped with a color, reflectivityor other sensor) that removes unwanted material. Screening can also beby magnetic screening wherein a magnet is disposed near the conveyedmaterial and the magnetic material is removed magnetically.

Optional pre-irradiation processing 752 can include heating thematerial. For example, a portion of the conveyor can be sent through aheated zone. The heated zone can be created, for example, by IRradiation, Microwaves, combustion (e.g., gas, coal, oil, biomass),resistive heating and/or inductive coils. The heat can be applied fromone side or more than one side, can be continuous or periodic and/or canbe for only a portion of the material or all the material. For example,a portion of the trough can be heated by use of a heating jacket.Heating can be, for example, for the purpose of drying the material. Inthe case of drying the material, this can also be facilitated, with orwithout heating, by the movement of a gas (e.g., air, nitrogen, oxygen,CO₂, Argon, He) over and/or through the biomass as it is being conveyed.Drying can also be in vacuo.

Pre-irradiation processing 752 can also be with reactive gases, forexample, ozone, ammonia, steam or a plasma. The gas can be suppliedabove atmospheric pressure.

Optionally, pre-irradiation processing 752 can include cooling thematerial. Cooling material is described in U.S. Pat. No. 7,900,857 filedJul. 14, 2009 and published Mar. 8, 2011, the entire disclosure of whichin incorporated herein by reference.

Another optional pre-irradiation processing 750 can include adding amaterial to the biomass. Vibratory conveying is very well suited to becoupled with the addition of a material, for example, by showering,sprinkling and or pouring a material onto the biomass as it is conveyed,because the vibratory conveyor provides agitation, tumbling and/orturning of the biomass that allows for efficient mixing and/orhomogenization of the biomass with any added material. Materials thatcan be added include, for example, metals, ceramics and/or ions asdescribed in U.S. application Ser. No. 12/605,534 and U.S. applicationSer. No. 12/639,289 the complete disclosures of which are incorporatedherein by reference. Other materials that can be added include acids,bases, oxidants (e.g., peroxides, chlorates), polymers, polymerizablemonomers (e.g., containing unsaturated bonds), water, catalysts, enzymesand/or organisms. Materials can be added, for example, in pure form, asa solution in a solvent (e.g., water or an organic solvent) and/or as asolution. In some cases the solvent is volatile and can be made toevaporate e.g., by heating and/or blowing gas as previously described.The added material may form a uniform coating on the biomass or be ahomogeneous mixture of different components (e.g., biomass andadditional material). The added material can modulate the subsequentirradiation step by increasing the efficiency of the irradiation,damping the irradiation or changing the effect of the irradiation (e.g.,from electron beams to X-rays or heat). The method may have no impact onthe irradiation but may be useful for further downstream processing. Theadded material may help in conveying the material, for example, bylowering dust levels.

After optional pre-radiation treatment the material is conveyed by thevibratory conveyor through an irradiation zone (e.g., the radiationfield) 754. Radiation can be by, for example, electron beam, ion beam,100 nm to 28 nm ultraviolet (UV) light, gamma or X-ray radiation. Forexample, radiation treatments and equipment are discussed below.Radiation treatments and systems for treatments are also discussed inU.S. Pat. No. 8,142,620, and U.S. patent application Ser. No.12/417,731, the entire disclosures of which are incorporated herein byreference.

Referring again to FIG. 7, after the biomass material has been conveyedthrough the radiation zone optional post processing 756 can be done. Theoptional post processing can, for example, be a process described withrespect to the pre-irradiation processing. For example, the biomass canbe screened, heated, cooled, and/or combined with additives. Uniquely topost-irradiation, quenching of the radicals can occur, for example,quenching of radicals by the addition of fluids (e.g., oxygen, reactiveliquids), using pressure, using heating and or addition of radicalscavengers. Quenching of biomass that has been irradiated is describedin U.S. Pat. No. 8,083,906 and issued Dec. 27, 2011 the disclosure ofwhich is incorporate herein by reference.

It may be advantageous to repeat irradiation to more thoroughly reducethe recalcitrance of the biomass. For example, as shown by path A inFIG. 7. In particular the process parameters might be adjusted after afirst (e.g., second, third, fourth or more) pass depending on therecalcitrance of the material. In some embodiments, the conveyor is aclosed circular system where the biomass is conveyed multiple timesthrough the various processes described above. In some other embodimentsmultiple irradiation devices (e.g., electron beam generators) are usedto irradiate the biomass multiple (e.g., 2, 3, 4 or more) times. In yetother embodiments, a single electron beam generator may be the source ofmultiple beams (e.g., 2, 3, 4 or more beams) that can be used forirradiation of the biomass.

Some more details and reiterations of processes for treating a feedstockthat can be utilized, for example, with the embodiments alreadydiscussed above, or in other embodiments, are described in the followingdisclosures.

Systems for Treating a Feedstock

Processes for conversion of a feedstock to sugars and other products, inwhich the conveying methods discuss above may be used, include, forexample, optionally physically pre-treating the feedstock, e.g., toreduce its size, before and/or after this treatment, optionally treatingthe feedstock to reduce its recalcitrance (e.g., by irradiation), andsaccharifying the feedstock to form a sugar solution. Saccharificationcan be performed by mixing a dispersion of the feedstock in a liquidmedium, e.g., water with an enzyme, as will be discussed in detailherein. Prior to treatment with an enzyme, pretreated biomass can besubjected to hot water and pressure, e.g., 100-150 deg C., 100-140, or110-130 deg C. and associated pressure. Prior to treatment with theenzyme the material is cooled to about 50 deg C. (e.g. between about 40and 60 deg C.). In addition or alternatively prior to the treatment withan enzyme the pretreated biomass can be treated with an acid, such ashydrochloric, sulfuric or phosphoric acid, e.g., less than 10%concentration (e.g., less than 5%, e.g. between about 0.01 and about 5%,between about 0.05 and about 1%, between about 0.05 and about 0.5%).During or after saccharification, the mixture (if saccharification is tobe partially or completely performed en route) or solution can betransported, e.g., by pipeline, railcar, truck or barge, to amanufacturing plant. At the plant, the solution can be bioprocessed,e.g., fermented, to produce a desired product or intermediate, which canthen be processed further, e.g., by distillation. The individualprocessing steps, materials used and examples of products andintermediates that may be formed will be described in detail below.

Radiation Treatment

The feedstock can be treated with radiation to modify its structure toreduce its recalcitrance. Such treatment can, for example, reduce theaverage molecular weight of the feedstock, change the crystallinestructure of the feedstock, and/or increase the surface area and/orporosity of the feedstock. Radiation can be by, for example, electronbeam, ion beam, 100 nm to 28 nm ultraviolet (UV) light, gamma or X-rayradiation. Radiation treatments and systems for treatments are discussedin U.S. Pat. No. 8,142,620, and U.S. patent application Ser. No.12/417,731, the entire disclosures of which are incorporated herein byreference.

Each form of radiation ionizes the biomass via particular interactions,as determined by the energy of the radiation. Heavy charged particlesprimarily ionize matter via Coulomb scattering; furthermore, theseinteractions produce energetic electrons that may further ionize matter.Alpha particles are identical to the nucleus of a helium atom and areproduced by the alpha decay of various radioactive nuclei, such asisotopes of bismuth, polonium, astatine, radon, francium, radium,several actinides, such as actinium, thorium, uranium, neptunium,curium, californium, americium, and plutonium. Electrons interact viaCoulomb scattering and bremsstrahlung radiation produced by changes inthe velocity of electrons.

When particles are utilized, they can be neutral (uncharged), positivelycharged or negatively charged. When charged, the charged particles canbear a single positive or negative charge, or multiple charges, e.g.,one, two, three or even four or more charges. In instances in whichchain scission is desired to change the molecular structure of thecarbohydrate containing material, positively charged particles may bedesirable, in part, due to their acidic nature. When particles areutilized, the particles can have the mass of a resting electron, orgreater, e.g., 500, 1000, 1500, or 2000 or more times the mass of aresting electron. For example, the particles can have a mass of fromabout 1 atomic unit to about 150 atomic units, e.g., from about 1 atomicunit to about 50 atomic units, or from about 1 to about 25, e.g., 1, 2,3, 4, 5, 10, 12 or 15 atomic units. Gamma radiation has the advantage ofa significant penetration depth into a variety of material in thesample.

In embodiments in which the irradiating is performed withelectromagnetic radiation, the electromagnetic radiation can have, e.g.,energy per photon (in electron volts) of greater than 10² eV, e.g.,greater than 10³, 10⁴, 10⁵, 10⁶, or even greater than 10⁷ eV. In someembodiments, the electromagnetic radiation has energy per photon ofbetween 10⁴ and 10⁷, e.g., between 10⁵ and 10⁶ eV. The electromagneticradiation can have a frequency of, e.g., greater than 10¹⁶ Hz, greaterthan 10¹⁷ Hz, 10¹⁸, 10¹⁹, 10²⁰, or even greater than 10²¹ Hz. In someembodiments, the electromagnetic radiation has a frequency of between10¹⁸ and 10²² Hz, e.g., between 10¹⁹ to 10²¹ Hz.

Electron bombardment may be performed using an electron beam device thathas a nominal energy of less than 10 MeV, e.g., less than 7 MeV, lessthan 5 MeV, or less than 2 MeV, e.g., from about 0.5 to about 4 MeV,from about 0.6 to about 3 MeV, from about 0.5 to 1.5 MeV, from about 0.8to 1.8 MeV, from about 0.7 to about 2.5 MeV, or from about 0.7 to 1 MeV.In some implementations the nominal energy is about 500 to 800 keV.

The electron beam may have a relatively high total beam power (thecombined beam power of all accelerating heads, or, if multipleaccelerators are used, of all accelerators and all heads), e.g., atleast 25 kW, e.g., at least 30, 40, 50, 60, 65, 70, 80, 100, 125, or 150kW. In some cases, the power is even as high as 500 kW, 750 kW, or even1000 kW or more. In some cases the electron beam has a beam power of1200 kW or more, e.g., 1400, 1600, 1800, or even 300 kW.

This high total beam power is usually achieved by utilizing multipleaccelerating heads. For example, the electron beam device may includetwo, four, or more accelerating heads. The use of multiple heads, eachof which has a relatively low beam power, prevents excessive temperaturerise in the material, thereby preventing burning of the material, andalso increases the uniformity of the dose through the thickness of thelayer of material.

It is generally preferred that the bed of biomass material has arelatively uniform thickness. In some embodiments the thickness is lessthan about 1 inch (e.g., less than about 0.75 inches, less than about0.5 inches, less than about 0.25 inches, less than about 0.1 inches,between about 0.1 and 1 inch, between about 0.2 and 0.3 inches).

It is desirable to treat the material as quickly as possible. Ingeneral, it is preferred that treatment be performed at a dose rate ofgreater than about 0.25 Mrad per second, e.g., greater than about 0.5,0.75, 1, 1.5, 2, 5, 7, 10, 12, 15, or even greater than about 20 Mradper second, e.g., about 0.25 to 2 Mrad per second. Higher dose ratesallow a higher throughput for a target (e.g., the desired) dose. Higherdose rates generally require higher line speeds, to avoid thermaldecomposition of the material. In one implementation, the accelerator isset for 3 MeV, 50 mA beam current, and the line speed is 24 feet/minute,for a sample thickness of about 20 mm (e.g., comminuted corn cobmaterial with a bulk density of 0.5 g/cm³).

In some embodiments, electron bombardment is performed until thematerial receives a total dose of at least 0.1 Mrad, 0.25 Mrad, 1 Mrad,5 Mrad, e.g., at least 10, 20, 30 or at least 40 Mrad. In someembodiments, the treatment is performed until the material receives adose of from about 10 Mrad to about 50 Mrad, e.g., from about 10 toabout 40 Mrad, from about 20 Mrad to about 40 Mrad, or from about 25Mrad to about 30 Mrad. In some implementations, a total dose of 25 to 35Mrad is preferred, applied ideally over a couple of passes, e.g., at 5Mrad/pass with each pass being applied for about one second. Coolingmethods such as cooling screw conveyors and cooled conveying troughs canalso be utilized, for example, after each irradiation, after the totalirradiation, during irradiation and/or before irradiation.

Using multiple heads as discussed above, the material can be treated inmultiple passes, for example, two passes at 10 to 20 Mrad/pass, e.g., 12to 18 Mrad/pass, separated by a few seconds of cool-down, or threepasses of 7 to 12 Mrad/pass, e.g., 5 to 20 Mrad/pass, 10 to 40Mrad/pass, 9 to 11 Mrad/pass. As discussed herein, treating the materialwith several relatively low doses, rather than one high dose, tends toprevent overheating of the material and also increases dose uniformitythrough the thickness of the material. In some implementations, thematerial is stirred or otherwise mixed during or after each pass andthen smoothed into a uniform layer again before the next pass, tofurther enhance treatment uniformity.

In some embodiments, electrons are accelerated to, for example, a speedof greater than 75 percent of the speed of light, e.g., greater than 85,90, 95, or 99 percent of the speed of light.

In some embodiments, any processing described herein occurs onlignocellulosic material that remains dry as acquired or that has beendried, e.g., using heat and/or reduced pressure. For example, in someembodiments, the cellulosic and/or lignocellulosic material has lessthan about 25 wt. % retained water, measured at 25° C. and at fiftypercent relative humidity (e.g., less than about 20 wt. %, less thanabout 15 wt. %, less than about 14 wt. %, less than about 13 wt. %, lessthan about 12 wt. %, less than about 10 wt. %, less than about 9 wt. %,less than about 8 wt. %, less than about 7 wt. %, less than about 6 wt.%, less than about 5 wt. %, less than about 4 wt. %, less than about 3wt. %, less than about 2 wt. %, less than about 1 wt. %, or less thanabout 0.5 wt. %.

In some embodiments, two or more ionizing sources can be used, such astwo or more electron sources. For example, samples can be treated, inany order, with a beam of electrons, followed by gamma radiation and UVlight having wavelengths from about 100 nm to about 280 nm. In someembodiments, samples are treated with three ionizing radiation sources,such as a beam of electrons, gamma radiation, and energetic UV light.The biomass is conveyed through the treatment zone where it can bebombarded with electrons.

It may be advantageous to repeat the treatment to more thoroughly reducethe recalcitrance of the biomass and/or further modify the biomass. Inparticular the process parameters can be adjusted after a first (e.g.,second, third, fourth or more) pass depending on the recalcitrance ofthe material. In some embodiments, a conveyor can be used which includesa circular system where the biomass is conveyed multiple times throughthe various processes described above. In some other embodimentsmultiple treatment devices (e.g., electron beam generators) are used totreat the biomass multiple (e.g., 2, 3, 4 or more) times. In yet otherembodiments, a single electron beam generator may be the source ofmultiple beams (e.g., 2, 3, 4 or more beams) that can be used fortreatment of the biomass.

The effectiveness in changing the molecular/supermolecular structureand/or reducing the recalcitrance of the carbohydrate-containing biomassdepends on the electron energy used and the dose applied, while exposuretime depends on the power and dose. In some embodiments, the dose rateand total dose are adjusted so as not to destroy (e.g., char or burn)the biomass material. For example, the carbohydrates should not bedamaged in the processing so that they can be released from the biomassintact, e.g. as monomeric sugars.

In some embodiments, the treatment (with any electron source or acombination of sources) is performed until the material receives a doseof at least about 0.05 Mrad, e.g., at least about 0.1, 0.25, 0.5, 0.75,1.0, 2.5, 5.0, 7.5, 10.0, 15, 20, 25, 30, 40, 50, 60, 70, 80, 90, 100,125, 150, 175, or 200 Mrad. In some embodiments, the treatment isperformed until the material receives a dose of between 0.1-100 Mrad,1-200, 5-200, 10-200, 5-150, 50-150 Mrad, 5-100, 5-50, 5-40, 10-50,10-75, 15-50, 20-35 Mrad.

In some embodiments, relatively low doses of radiation are utilized,e.g., to increase the molecular weight of a cellulosic orlignocellulosic material (with any radiation source or a combination ofsources described herein). For example, a dose of at least about 0.05Mrad, e.g., at least about 0.1 Mrad or at least about 0.25, 0.5, 0.75.1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, or at least about 5.0 Mrad. In someembodiments, the irradiation is performed until the material receives adose of between 0.1 Mrad and 2.0 Mrad, e.g., between 0.5 rad and 4.0Mrad or between 1.0 Mrad and 3.0 Mrad.

It also can be desirable to irradiate from multiple directions,simultaneously or sequentially, in order to achieve a desired degree ofpenetration of radiation into the material. For example, depending onthe density and moisture content of the material, such as wood, and thetype of radiation source used (e.g., gamma or electron beam), themaximum penetration of radiation into the material may be only about0.75 inch. In such a case, a thicker section (up to 1.5 inch) can beirradiated by first irradiating the material from one side, and thenturning the material over and irradiating from the other side.Irradiation from multiple directions can be particularly useful withelectron beam radiation, which irradiates faster than gamma radiationbut typically does not achieve as great a penetration depth.

Radiation Opaque Materials

As previously discussed, the invention can include processing thematerial in a vault and/or bunker that is constructed using radiationopaque materials. In some implementations, the radiation opaquematerials are selected to be capable of shielding the components fromX-rays with high energy (short wavelength), which can penetrate manymaterials. One important factor in designing a radiation shieldingenclosure is the attenuation length of the materials used, which willdetermine the required thickness for a particular material, blend ofmaterials, or layered structure. The attenuation length is thepenetration distance at which the radiation is reduced to approximately1/e (e=Eulers number) times that of the incident radiation. Althoughvirtually all materials are radiation opaque if thick enough, materialscontaining a high compositional percentage (e.g., density) of elementsthat have a high Z value (atomic number) have a shorter radiationattenuation length and thus if such materials are used a thinner,lighter shielding can be provided. Examples of high Z value materialsthat are used in radiation shielding are tantalum and lead. Anotherimportant parameter in radiation shielding is the halving distance,which is the thickness of a particular material that will reduce gammaray intensity by 50%. As an example for X-ray radiation with an energyof 0.1 MeV the halving thickness is about 15.1 mm for concrete and about2.7 mm for lead, while with an X-ray energy of 1 MeV the halvingthickness for concrete is about 44.45 mm and for lead is about 7.9 mm.Radiation opaque materials can be materials that are thick or thin solong as they can reduce the radiation that passes through to the otherside. Thus, if it is desired that a particular enclosure have a low wallthickness, e.g., for light weight or due to size constraints, thematerial chosen should have a sufficient Z value and/or attenuationlength so that its halving length is less than or equal to the desiredwall thickness of the enclosure.

In some cases, the radiation opaque material may be a layered material,for example, having a layer of a higher Z value material, to providegood shielding, and a layer of a lower Z value material to provide otherproperties (e.g., structural integrity, impact resistance, etc.). Insome cases, the layered material may be a “graded-Z” laminate, e.g.,including a laminate in which the layers provide a gradient from high-Zthrough successively lower-Z elements. In some cases the radiationopaque materials can be interlocking blocks, for example, lead and/orconcrete blocks can be supplied by NELCO Worldwide (Burlington, Mass.),and reconfigurable vaults can be utilized.

A radiation opaque material can reduce the radiation passing through astructure (e.g., a wall, door, ceiling, enclosure, a series of these orcombinations of these) formed of the material by about at least about10%, (e.g., at least about 20%, at least about 30%, at least about 40%,at least about 50%, at least about 60%, at least about 70%, at leastabout 80%, at least about 90%, at least about 95%, at least about 96%,at least about 97%, at least about 98%, at least about 99%, at leastabout 99.9%, at least about 99.99%, at least about 99.999%) as comparedto the incident radiation. Therefore, an enclosure made of a radiationopaque material can reduce the exposure of equipment/system/componentsby the same amount. Radiation opaque materials can include stainlesssteel, metals with Z values above 25 (e.g., lead, iron), concrete, dirt,sand and combinations thereof. Radiation opaque materials can include abarrier in the direction of the incident radiation of at least about 1mm (e.g., 5 mm, 10 mm, 5 cm, 10 cm, 100 cm, 1 m, 10 m).

Radiation Sources

The type of radiation determines the kinds of radiation sources used aswell as the radiation devices and associated equipment. The methods,systems and equipment described herein, for example, for treatingmaterials with radiation, can utilized sources as described herein aswell as any other useful source.

Sources of gamma rays include radioactive nuclei, such as isotopes ofcobalt, calcium, technetium, chromium, gallium, indium, iodine, iron,krypton, samarium, selenium, sodium, thallium, and xenon.

Sources of X-rays include electron beam collision with metal targets,such as tungsten or molybdenum or alloys, or compact light sources, suchas those produced commercially by Lyncean.

Alpha particles are identical to the nucleus of a helium atom and areproduced by the alpha decay of various radioactive nuclei, such asisotopes of bismuth, polonium, astatine, radon, francium, radium,several actinides, such as actinium, thorium, uranium, neptunium,curium, californium, americium, and plutonium.

Sources for ultraviolet radiation include deuterium or cadmium lamps.

Sources for infrared radiation include sapphire, zinc, or selenidewindow ceramic lamps.

Sources for microwaves include klystrons, Slevin type RF sources, oratom beam sources that employ hydrogen, oxygen, or nitrogen gases.

Accelerators used to accelerate the particles (e.g., electrons or ions)can be DE (e.g., electrostatic DC, electrodynamic DC), RF linear,magnetic induction linear or continuous wave. For example, variousirradiating devices may be used in the methods disclosed herein,including field ionization sources, electrostatic ion separators, fieldionization generators, thermionic emission sources, microwave dischargeion sources, recirculating or static accelerators, dynamic linearaccelerators, van de Graaff accelerators, Cockroft Walton accelerators(e.g., PELLETRON® accelerators), LINACS, Dynamitrons (e.g, DYNAMITRON®accelerators), cyclotrons, synchrotrons, betatrons, transformer-typeaccelerators, microtrons, plasma generators, cascade accelerators, andfolded tandem accelerators. For example, cyclotron type accelerators areavailable from IBA, Belgium, such as the RHODOTRON™ system, while DCtype accelerators are available from RDI, now IBA Industrial, such asthe DYNAMITRON®. Other suitable accelerator systems include, forexample: DC insulated core transformer (ICT) type systems, availablefrom Nissin High Voltage, Japan; S-band LINACs, available from L3-PSD(USA), Linac Systems (France), Mevex (Canada), and Mitsubishi HeavyIndustries (Japan); L-band LINACs, available from Iotron Industries(Canada); and ILU-based accelerators, available from Budker Laboratories(Russia). Ions and ion accelerators are discussed in IntroductoryNuclear Physics, Kenneth S. Krane, John Wiley & Sons, Inc. (1988), KrstoPrelec, FIZIKA B 6 (1997) 4, 177-206, Chu, William T., “Overview ofLight-Ion Beam Therapy”, Columbus-Ohio, ICRU-IAEA Meeting, 18-20 Mar.2006, Iwata, Y. et al., “Alternating-Phase-Focused IH-DTL for Heavy-IonMedical Accelerators”, Proceedings of EPAC 2006, Edinburgh, Scotland,and Leitner, C. M. et al., “Status of the Superconducting ECR Ion SourceVenus”, Proceedings of EPAC 2000, Vienna, Austria. Some particleaccelerators and their uses are disclosed, for example, in U.S. Pat. No.7,931,784 to Medoff, the complete disclosure of which is incorporatedherein by reference.

Electrons may be produced by radioactive nuclei that undergo beta decay,such as isotopes of iodine, cesium, technetium, and iridium.Alternatively, an electron gun can be used as an electron source viathermionic emission and accelerated through an accelerating potential.An electron gun generates electrons, which are then accelerated througha large potential (e.g., greater than about 500 thousand, greater thanabout 1 million, greater than about 2 million, greater than about 5million, greater than about 6 million, greater than about 7 million,greater than about 8 million, greater than about 9 million, or evengreater than 10 million volts) and then scanned magnetically in the x-yplane, where the electrons are initially accelerated in the z directiondown the accelerator tube and extracted through a foil window. Scanningthe electron beams is useful for increasing the irradiation surface whenirradiating materials, e.g., a biomass, that is conveyed through thescanned beam. Scanning the electron beam also distributes the thermalload homogenously on the window and helps reduce the foil window rupturedue to local heating by the electron beam. Window foil rupture is acause of significant down-time due to subsequent necessary repairs andre-starting the electron gun.

A beam of electrons can be used as the radiation source. A beam ofelectrons has the advantages of high dose rates (e.g., 1, 5, or even 10Mrad per second), high throughput, less containment, and lessconfinement equipment. Electron beams can also have high electricalefficiency (e.g., 80%), allowing for lower energy usage relative toother radiation methods, which can translate into a lower cost ofoperation and lower greenhouse gas emissions corresponding to thesmaller amount of energy used. Electron beams can be generated, e.g., byelectrostatic generators, cascade generators, transformer generators,low energy accelerators with a scanning system, low energy acceleratorswith a linear cathode, linear accelerators, and pulsed accelerators.

Electrons can also be more efficient at causing changes in the molecularstructure of carbohydrate-containing materials, for example, by themechanism of chain scission. In addition, electrons having energies of0.5-10 MeV can penetrate low density materials, such as the biomassmaterials described herein, e.g., materials having a bulk density ofless than 0.5 g/cm³, and a depth of 0.3-10 cm. Electrons as an ionizingradiation source can be useful, e.g., for relatively thin piles, layersor beds of materials, e.g., less than about 0.5 inch, e.g., less thanabout 0.4 inch, 0.3 inch, 0.25 inch, or less than about 0.1 inch. Insome embodiments, the energy of each electron of the electron beam isfrom about 0.3 MeV to about 2.0 MeV (million electron volts), e.g., fromabout 0.5 MeV to about 1.5 MeV, or from about 0.7 MeV to about 1.25 MeV.Methods of irradiating materials are discussed in U.S. Pat. App. Pub.2012/0100577 A1, filed Oct. 18, 2011, the entire disclosure of which isherein incorporated by reference.

Electron beam irradiation devices may be procured commercially or built.For example, elements or components such inductors, capacitors, casings,power sources, cables, wiring, voltage control systems, current controlelements, insulating material, microcontrollers and cooling equipmentcan be purchased and assembled into a device. Optionally, a commercialdevice can be modified and/or adapted. For example, devices andcomponents can be purchased from any of the commercial sources describedherein including Ion Beam Applications (Louvain-la-Neuve, Belgium), NHVCorporation (Japan), the Titan Corporation (San Diego, Calif.), ViviradHigh Voltage Corp (Billerica, Mass.) and/or Budker Laboratories(Russia). Typical electron energies can be 0.5 MeV, 1 MeV, 2 MeV, 4.5MeV, 7.5 MeV, or 10 MeV. Typical electron beam irradiation device powercan be 1 kW, 5 kW, 10 kW, 20 kW, 50 kW, 60 kW, 70 kW, 80 kW, 90 kW, 100kW, 125 kW, 150 kW, 175 kW, 200 kW, 250 kW, 300 kW, 350 kW, 400 kW, 450kW, 500 kW, 600 kW, 700 kW, 800 kW, 900 kW or even 1000 kW. Acceleratorsthat can be used include NHV irradiators medium energy series EPS-500(e.g., 500 kV accelerator voltage and 65, 100 or 150 mA beam current),EPS-800 (e.g., 800 kV accelerator voltage and 65 or 100 mA beamcurrent), or EPS-1000 (e.g., 1000 kV accelerator voltage and 65 or 100mA beam current). Also, accelerators from NHV's high energy series canbe used such as EPS-1500 (e.g., 1500 kV accelerator voltage and 65 mAbeam current), EPS-2000 (e.g., 2000 kV accelerator voltage and 50 mAbeam current), EPS-3000 (e.g., 3000 kV accelerator voltage and 50 mAbeam current) and EPS-5000 (e.g., 5000 and 30 mA beam current).

Tradeoffs in considering electron beam irradiation device powerspecifications include cost to operate, capital costs, depreciation, anddevice footprint. Tradeoffs in considering exposure dose levels ofelectron beam irradiation would be energy costs and environment, safety,and health (ESH) concerns. Typically, generators are housed in a vault,e.g., of lead or concrete, especially for production from X-rays thatare generated in the process. Tradeoffs in considering electron energiesinclude energy costs.

The electron beam irradiation device can produce either a fixed beam ora scanning beam. A scanning beam may be advantageous with large scansweep length and high scan speeds, as this would effectively replace alarge, fixed beam width. Further, available sweep widths of 0.5 m, 1 m,2 m or more are available. The scanning beam is preferred in mostembodiments describe herein because of the larger scan width and reducedpossibility of local heating and failure of the windows.

Electron Guns—Windows

The extraction system for an electron accelerator can include two windowfoils. The cooling gas in the two foil window extraction system can be apurge gas or a mixture, for example, air, or a pure gas. In oneembodiment the gas is an inert gas such as nitrogen, argon, helium andor carbon dioxide. It is preferred to use a gas rather than a liquidsince energy losses to the electron beam are minimized. Mixtures of puregas can also be used, either pre-mixed or mixed in line prior toimpinging on the windows or in the space between the windows. Thecooling gas can be cooled, for example, by using a heat exchange system(e.g., a chiller) and/or by using boil off from a condensed gas (e.g.,liquid nitrogen, liquid helium).

Heating and Throughput During Radiation Treatment

Several processes can occur in biomass when electrons from an electronbeam interact with matter in inelastic collisions. For example,ionization of the material, chain scission of polymers in the material,cross linking of polymers in the material, oxidation of the material,generation of X-rays (“Bremsstrahlung”) and vibrational excitation ofmolecules (e.g. phonon generation). Without being bound to a particularmechanism, the reduction in recalcitrance can be due to several of theseinelastic collision effects, for example, ionization, chain scission ofpolymers, oxidation and phonon generation. Some of the effects (e.g.,especially X-ray generation), necessitate shielding and engineeringbarriers, for example, enclosing the irradiation processes in a concrete(or other radiation opaque material) vault. Another effect ofirradiation, vibrational excitation, is equivalent to heating up thesample. Heating the sample by irradiation can help in recalcitrancereduction, but excessive heating can destroy the material, as will beexplained below.

The adiabatic temperature rise (ΔT) from adsorption of ionizingradiation is given by the equation: ΔT=D/Cp: where D is the average dosein kGy, C_(p) is the heat capacity in J/g ° C., and ΔT is the change intemperature in ° C. A typical dry biomass material will have a heatcapacity close to 2. Wet biomass will have a higher heat capacitydependent on the amount of water since the heat capacity of water isvery high (4.19 J/g ° C.). Metals have much lower heat capacities, forexample, 304 stainless steel has a heat capacity of 0.5 J/g ° C. Thetemperature change due to the instant adsorption of radiation in abiomass and stainless steel for various doses of radiation is shown inTable 1.

TABLE 1 Calculated Temperature increase for biomass and stainless steel.Dose (Mrad) Estimated Biomass ΔT (° C.) Steel ΔT (° C.) 10 50 200 50 2501000 100 500 2000 150 750 3000 200 1000 4000

High temperatures can destroy and or modify the biopolymers in biomassso that the polymers (e.g., cellulose) are unsuitable for furtherprocessing. A biomass subjected to high temperatures can become dark,sticky and give off odors indicating decomposition. The stickiness caneven make the material hard to convey. The odors can be unpleasant andbe a safety issue. In fact, keeping the biomass below about 200° C. hasbeen found to be beneficial in the processes described herein (e.g.,below about 190° C., below about 180° C., below about 170° C., belowabout 160° C., below about 150° C., below about 140° C., below about130° C., below about 120° C., below about 110° C., between about 60° C.and 180° C., between about 60° C. and 160° C., between about 60° C. and150° C., between about 60° C. and 140° C., between about 60° C. and 130°C., between about 60° C. and 120° C., between about 80° C. and 180° C.,between about 100° C. and 180° C., between about 120° C. and 180° C.,between about 140° C. and 180° C., between about 160° C. and 180° C.,between about 100° C. and 140° C., between about 80° C. and 120° C.).

It has been found that irradiation above about 10 Mrad is desirable forthe processes described herein (e.g., reduction of recalcitrance). Ahigh throughput is also desirable so that the irradiation does notbecome a bottle neck in processing the biomass. The treatment isgoverned by a Dose rate equation: M=FP/D·time, where M is the mass ofirradiated material (Kg), F is the fraction of power that is adsorbed(unit less), P is the emitted power (kW=Voltage in MeV×Current in mA),time is the treatment time (sec) and D is the adsorbed dose (kGy). In anexemplary process where the fraction of adsorbed power is fixed, thePower emitted is constant and a set dosage is desired, the throughput(e.g., M, the biomass processed) can be increased by increasing theirradiation time. However, increasing the irradiation time withoutallowing the material to cool, can excessively heat the material asexemplified by the calculations shown above. Since biomass has a lowthermal conductivity (less than about 0.1 Wm⁻¹K⁻¹), heat dissipation isslow, unlike, for example, metals (greater than about 10 Wm⁻¹K⁻¹) whichcan dissipate energy quickly as long as there is a heat sink to transferthe energy to.

Electron Guns—Beam Stops

In some embodiments the systems and methods include a beam stop (e.g., ashutter). For example, the beam stop can be used to quickly stop orreduce the irradiation of material without powering down the electronbeam device. Alternatively the beam stop can be used while powering upthe electron beam, e.g., the beam stop can stop the electron beam untila beam current of a desired level is achieved. The beam stop can beplaced between the primary foil window and a secondary foil window. Forexample, the beam stop can be mounted so that it is movable, that is, sothat it can be moved into and out of the beam path. Even partialcoverage of the beam can be used, for example, to control the dose ofirradiation. The beam stop can be mounted to the floor, to a conveyorfor the biomass, to a wall, to the radiation device (e.g., at the scanhorn), or to any structural support. Preferably the beam stop is fixedin relation to the scan horn so that the beam can be effectivelycontrolled by the beam stop. The beam stop can incorporate a hinge, arail, wheels, slots, or other means allowing for its operation in movinginto and out of the beam. The beam stop can be made of any material thatwill stop at least 5% of the electrons, e.g., at least 10%, 20%, 30%,40%, 50%, 60%, 70%, at least 80%, 85%, 90%, 91%, 92%, 93%, 94%, 95%,96%, 97%, 98%, 99% or even about 100% of the electrons.

The beam stop can be made of a metal including, but not limited to,stainless steel, lead, iron, molybdenum, silver, gold, titanium,aluminum, tin, or alloys of these, or laminates (layered materials) madewith such metals (e.g., metal-coated ceramic, metal-coated polymer,metal-coated composite, multilayered metal materials).

The beam stop can be cooled, for example, with a cooling fluid such asan aqueous solution or a gas. The beam stop can be partially orcompletely hollow, for example, with cavities. Interior spaces of thebeam stop can be used for cooling fluids and gases. The beam stop can beof any shape, including flat, curved, round, oval, square, rectangular,beveled and wedged shapes.

The beam stop can have perforations so as to allow some electronsthrough, thus controlling (e.g., reducing) the levels of radiationacross the whole area of the window, or in specific regions of thewindow. The beam stop can be a mesh formed, for example, from fibers orwires. Multiple beam stops can be used, together or independently, tocontrol the irradiation. The beam stop can be remotely controlled, e.g.,by radio signal or hard wired to a motor for moving the beam into or outof position.

Beam Dumps

The embodiments disclosed herein can also include a beam dump. A beamdump's purpose is to safely absorb a beam of charged particles. Like abeam stop, a beam dump can be used to block the beam of chargedparticles. However, a beam dump is much more robust than a beam stop,and is intended to block the full power of the electron beam for anextended period of time. They are often used to block the beam as theaccelerator is powering up.

Beam dumps are also designed to accommodate the heat generated by suchbeams, and are usually made from materials such as copper, aluminum,carbon, beryllium, tungsten, or mercury. Beam dumps can be cooled, forexample, by using a cooling fluid that is in thermal contact with thebeam dump.

Biomass Materials

Lignocellulosic materials include, but are not limited to, wood,particle board, forestry wastes (e.g., sawdust, aspen wood, wood chips),grasses, (e.g., switchgrass, miscanthus, cord grass, reed canary grass),grain residues, (e.g., rice hulls, oat hulls, wheat chaff, barleyhulls), agricultural waste (e.g., silage, canola straw, wheat straw,barley straw, oat straw, rice straw, jute, hemp, flax, bamboo, sisal,abaca, corn cobs, corn stover, soybean stover, corn fiber, alfalfa, hay,coconut hair), sugar processing residues (e.g., bagasse, beet pulp,agave bagasse), algae, seaweed, manure, sewage, and mixtures of any ofthese.

In some cases, the lignocellulosic material includes corncobs. Ground orhammermilled corncobs can be spread in a layer of relatively uniformthickness for irradiation, and after irradiation are easy to disperse inthe medium for further processing. To facilitate harvest and collection,in some cases the entire corn plant is used, including the corn stalk,corn kernels, and in some cases even the root system of the plant.

Advantageously, no additional nutrients (other than a nitrogen source,e.g., urea or ammonia) are required during fermentation of corncobs orcellulosic or lignocellulosic materials containing significant amountsof corncobs.

Corncobs, before and after comminution, are also easier to convey anddisperse, and have a lesser tendency to form explosive mixtures in airthan other cellulosic or lignocellulosic materials such as hay andgrasses.

Cellulosic materials include, for example, paper, paper products, paperwaste, paper pulp, pigmented papers, loaded papers, coated papers,filled papers, magazines, printed matter (e.g., books, catalogs,manuals, labels, calendars, greeting cards, brochures, prospectuses,newsprint), printer paper, polycoated paper, card stock, cardboard,paperboard, materials having a high α-cellulose content such as cotton,and mixtures of any of these. For example, paper products as describedin U.S. application Ser. No. 13/396,365 (“Magazine Feedstocks” by Medoffet al., filed Feb. 14, 2012), the full disclosure of which isincorporated herein by reference.

Cellulosic materials can also include lignocellulosic materials whichhave been partially or fully de-lignified.

In some instances other biomass materials can be utilized, for example,starchy materials. Starchy materials include starch itself, e.g., cornstarch, wheat starch, potato starch or rice starch, a derivative ofstarch, or a material that includes starch, such as an edible foodproduct or a crop. For example, the starchy material can be arracacha,buckwheat, banana, barley, cassava, kudzu, ocra, sago, sorghum, regularhousehold potatoes, sweet potato, taro, yams, or one or more beans, suchas favas, lentils or peas. Blends of any two or more starchy materialsare also starchy materials. Mixtures of starchy, cellulosic and orlignocellulosic materials can also be used. For example, a biomass canbe an entire plant, a part of a plant or different parts of a plant,e.g., a wheat plant, cotton plant, a corn plant, rice plant or a tree.The starchy materials can be treated by any of the methods describedherein.

Microbial materials that can be used as feedstock can include, but arenot limited to, any naturally occurring or genetically modifiedmicroorganism or organism that contains or is capable of providing asource of carbohydrates (e.g., cellulose), for example, protists, e.g.,animal protists (e.g., protozoa such as flagellates, amoeboids,ciliates, and sporozoa) and plant protists (e.g., algae such alveolates,chlorarachniophytes, cryptomonads, euglenids, glaucophytes, haptophytes,red algae, stramenopiles, and viridaeplantae). Other examples includeseaweed, plankton (e.g., macroplankton, mesoplankton, microplankton,nanoplankton, picoplankton, and femtoplankton), phytoplankton, bacteria(e.g., gram positive bacteria, gram negative bacteria, andextremophiles), yeast and/or mixtures of these. In some instances,microbial biomass can be obtained from natural sources, e.g., the ocean,lakes, bodies of water, e.g., salt water or fresh water, or on land.Alternatively or in addition, microbial biomass can be obtained fromculture systems, e.g., large scale dry and wet culture and fermentationsystems.

In other embodiments, the biomass materials, such as cellulosic, starchyand lignocellulosic feedstock materials, can be obtained from transgenicmicroorganisms and plants that have been modified with respect to a wildtype variety. Such modifications may be, for example, through theiterative steps of selection and breeding to obtain desired traits in aplant. Furthermore, the plants can have had genetic material removed,modified, silenced and/or added with respect to the wild type variety.For example, genetically modified plants can be produced by recombinantDNA methods, where genetic modifications include introducing ormodifying specific genes from parental varieties, or, for example, byusing transgenic breeding wherein a specific gene or genes areintroduced to a plant from a different species of plant and/or bacteria.Another way to create genetic variation is through mutation breedingwherein new alleles are artificially created from endogenous genes. Theartificial genes can be created by a variety of ways including treatingthe plant or seeds with, for example, chemical mutagens (e.g., usingalkylating agents, epoxides, alkaloids, peroxides, formaldehyde),irradiation (e.g., X-rays, gamma rays, neutrons, beta particles, alphaparticles, protons, deuterons, UV radiation) and temperature shocking orother external stressing and subsequent selection techniques. Othermethods of providing modified genes is through error prone PCR and DNAshuffling followed by insertion of the desired modified DNA into thedesired plant or seed. Methods of introducing the desired geneticvariation in the seed or plant include, for example, the use of abacterial carrier, biolistics, calcium phosphate precipitation,electroporation, gene splicing, gene silencing, lipofection,microinjection and viral carriers. Additional genetically modifiedmaterials have been described in U.S. application Ser. No. 13/396,369filed Feb. 14, 2012 the full disclosure of which is incorporated hereinby reference.

Any of the methods described herein can be practiced with mixtures ofany biomass materials described herein.

Other Materials

Other materials (e.g., natural or synthetic materials), for example,polymers, can be treated and/or made utilizing the methods, equipmentand systems described herein. For example, polyethylene (e.g., linearlow density ethylene and high density polyethylene), polystyrenes,sulfonated polystyrenes, poly (vinyl chloride), polyesters (e.g.,nylons, DACRON™, KODEL™), polyalkylene esters, poly vinyl esters,polyamides (e.g., KEVLAR™) polyethylene terephthalate, celluloseacetate, acetal, poly acrylonitrile, polycarbonates (e.g., LEXAN™),acrylics [e.g., poly (methyl methacrylate), poly(methyl methacrylate),polyacrylnitriles], Poly urethanes, polypropylene, poly butadiene,polyisobutylene, polyacrylonitrile, polychloroprene (e.g. neoprene),poly(cis-1,4-isoprene) [e.g., natural rubber], poly(trans-1,4-isoprene)[e.g., gutta percha], phenol formaldehyde, melamine formaldehyde,epoxides, polyesters, poly amines, polycarboxylic acids, polylacticacids, polyvinyl alcohols, polyanhydrides, poly fluoro carbons (e.g.,TEFLON™), silicons (e.g., silicone rubber), polysilanes, poly ethers(e.g., polyethylene oxide, polypropylene oxide), waxes, oils andmixtures of these. Also included are plastics, rubbers, elastomers,fibers, waxes, gels, oils, adhesives, thermoplastics, thermosets,biodegradable polymers, resins made with these polymers, other polymers,other materials and combinations thereof. The polymers can be made byany useful method including cationic polymerization, anionicpolymerization, radical polymerization, metathesis polymerization, ringopening polymerization, graft polymerization, addition polymerization.In some cases the treatments disclosed herein can be used, for example,for radically initiated graft polymerization and cross linking.Composites of polymers, for example, with glass, metals, biomass (e.g.,fibers, particles), ceramics can also be treated and/or made.

Other materials that can be treated by using the methods, systems andequipment disclosed herein are ceramic materials, minerals, metals,inorganic compounds. For example, silicon and germanium crystals,silicon nitrides, metal oxides, semiconductors, insulators, cements andor conductors.

In addition, manufactured multipart or shaped materials (e.g., molded,extruded, welded, riveted, layered or combined in any way) can betreated, for example, cables, pipes, boards, enclosures, integratedsemiconductor chips, circuit boards, wires, tires, windows, laminatedmaterials, gears, belts, machines, combinations of these. For example,treating a material by the methods described herein can modify thesurfaces, for example, making them susceptible to furtherfunctionalization, combinations (e.g., welding) and/or treatment cancross link the materials.

Biomass Material Preparation—Mechanical Treatments

The biomass can be in a dry form, for example, with less than about 35%moisture content (e.g., less than about 20%, less than about 15%, lessthan about 10% less than about 5%, less than about 4%, less than about3%, less than about 2% or even less than about 1%). The biomass can alsobe delivered in a wet state, for example, as a wet solid, a slurry or asuspension with at least about 10 wt. % solids (e.g., at least about 20wt. %, at least about 30 wt. %, at least about 40 wt. %, at least about50 wt. %, at least about 60 wt. %, at least about 70 wt. %).

The material to be processed, e.g., biomass material, can be aparticulate material. For example, with an average particle size aboveat least about 0.25 mm (e.g., at least about 0.5 mm, at least about 0.75mm) and below about 6 mm (e.g., below about 3 mm, below about 2 mm). Insome embodiments this is produced by mechanical means, for example, asdescribed herein.

The processes disclosed herein can utilize low bulk density materials,for example, cellulosic or lignocellulosic feedstocks that have beenphysically pretreated to have a bulk density of less than about 0.75g/cm³, e.g., less than about 0.7, 0.65, 0.60, 0.50, 0.35, 0.25, 0.20,0.15, 0.10, 0.05 or less, e.g., less than about 0.025 g/cm³. Bulkdensity is determined using ASTM D1895B. Briefly, the method involvesfilling a measuring cylinder of known volume with a sample and obtaininga weight of the sample. The bulk density is calculated by dividing theweight of the sample in grams by the known volume of the cylinder incubic centimeters. If desired, low bulk density materials can bedensified, for example, by methods described in U.S. Pat. No. 7,971,809published Jul. 5, 2011, the entire disclosure of which is herebyincorporated by reference.

In some cases, the pre-treatment processing includes screening of thebiomass material. Screening can be through a mesh or perforated platewith a desired opening size, for example, less than about 6.35 mm (¼inch, 0.25 inch), (e.g., less than about 3.18 mm (⅛ inch, 0.125 inch),less than about 1.59 mm ( 1/16 inch, 0.0625 inch), is less than about0.79 mm ( 1/32 inch, 0.03125 inch), e.g., less than about 0.51 mm ( 1/50inch, 0.02000 inch), less than about 0.40 mm ( 1/64 inch, 0.015625inch), less than about 0.23 mm (0.009 inch), less than about 0.20 mm (1/128 inch, 0.0078125 inch), less than about 0.18 mm (0.007 inch), lessthan about 0.13 mm (0.005 inch), or even less than about 0.10 mm ( 1/256inch, 0.00390625 inch)). In one configuration the desired biomass fallsthrough the perforations or screen and thus biomass larger than theperforations or screen are not irradiated. These larger materials can bere-processed, for example, by comminuting, or they can simply be removedfrom processing. In another configuration material that is larger thanthe perforations is irradiated and the smaller material is removed bythe screening process or recycled. In this kind of a configuration, theconveyor, such as a vibratory conveyor, itself (for example, a part ofthe conveyor) can be perforated or made with a mesh. For example, in oneparticular embodiment the biomass material may be wet and theperforations or mesh allow water to drain away from the biomass beforeirradiation.

Screening of material can also be by a manual method, for example, by anoperator or mechanoid (e.g., a robot equipped with a color, reflectivityor other sensor) that removes unwanted material. Screening can also beby magnetic screening wherein a magnet is disposed near the conveyedmaterial and the magnetic material is removed magnetically.

Optional pre-treatment processing can include heating the material. Forexample, a portion of a conveyor conveying the biomass or other materialcan be sent through a heated zone. The heated zone can be created, forexample, by IR radiation, microwaves, combustion (e.g., gas, coal, oil,biomass), resistive heating and/or inductive coils. The heat can beapplied from at least one side or more than one side, can be continuousor periodic and can be for only a portion of the material or all thematerial. For example, a portion of the conveying trough can be heatedby use of a heating jacket. Heating can be, for example, for the purposeof drying the material. In the case of drying the material, this canalso be facilitated, with or without heating, by the movement of a gas(e.g., air, oxygen, nitrogen, He, CO₂, Argon) over and/or through thebiomass as it is being conveyed.

Optionally, pre-treatment processing can include cooling the material.Cooling material is described in U.S. Pat. No. 7,900,857 published Mar.8, 2011, the disclosure of which in incorporated herein by reference.For example, cooling can be by supplying a cooling fluid, for example,water (e.g., with glycerol), or nitrogen (e.g., liquid nitrogen) to thebottom of the conveying trough. Alternatively, a cooling gas, forexample, chilled nitrogen can be blown over the biomass materials orunder the conveying system.

Another optional pre-treatment processing method can include adding amaterial to the biomass or other feedstocks. The additional material canbe added by, for example, by showering, sprinkling and or pouring thematerial onto the biomass as it is conveyed. Materials that can be addedinclude, for example, metals, ceramics and/or ions as described in U.S.Patent App. Pub. 2010/0105119 A1 (filed Oct. 26, 2009) and U.S. PatentApp. Pub. 2010/0159569 A1 (filed Dec. 16, 2009), the entire disclosuresof which are incorporated herein by reference. Optional materials thatcan be added include acids and bases. Other materials that can be addedare oxidants (e.g., peroxides, chlorates), polymers, polymerizablemonomers (e.g., containing unsaturated bonds), water, catalysts, enzymesand/or organisms. Materials can be added, for example, in pure form, asa solution in a solvent (e.g., water or an organic solvent) and/or as asolution. In some cases the solvent is volatile and can be made toevaporate e.g., by heating and/or blowing gas as previously described.The added material may form a uniform coating on the biomass or be ahomogeneous mixture of different components (e.g., biomass andadditional material). The added material can modulate the subsequentirradiation step by increasing the efficiency of the irradiation,damping the irradiation or changing the effect of the irradiation (e.g.,from electron beams to X-rays or heat). The method may have no impact onthe irradiation but may be useful for further downstream processing. Theadded material may help in conveying the material, for example, bylowering dust levels.

Biomass can be delivered to conveyor (e.g., vibratory conveyors that canbe used in the vaults herein described) by a belt conveyor, a pneumaticconveyor, a screw conveyor, a hopper, a pipe, manually or by acombination of these. The biomass can, for example, be dropped, pouredand/or placed onto the conveyor by any of these methods. In someembodiments the material is delivered to the conveyor using an enclosedmaterial distribution system to help maintain a low oxygen atmosphereand/or control dust and fines. Lofted or air suspended biomass fines anddust are undesirable because these can form an explosion hazard ordamage the window foils of an electron gun (if such a device is used fortreating the material).

The material can be leveled to form a uniform thickness between about0.0312 and 5 inches (e.g., between about 0.0625 and 2.000 inches,between about 0.125 and 1 inches, between about 0.125 and 0.5 inches,between about 0.3 and 0.9 inches, between about 0.2 and 0.5 inchesbetween about 0.25 and 1.0 inches, between about 0.25 and 0.5 inches,0.100+/−0.025 inches, 0.150+/−0.025 inches, 0.200+/−0.025 inches,0.250+/−0.025 inches, 0.300+/−0.025 inches, 0.350+/−0.025 inches,0.400+/−0.025 inches, 0.450+/−0.025 inches, 0.500+/−0.025 inches,0.550+/−0.025 inches, 0.600+/−0.025 inches, 0.700+/−0.025 inches,0.750+/−0.025 inches, 0.800+/−0.025 inches, 0.850+/−0.025 inches,0.900+/−0.025 inches, 0.900+/−0.025 inches.

Generally, it is preferred to convey the material as quickly as possiblethrough the electron beam to maximize throughput. For example, thematerial can be conveyed at rates of at least 1 ft/min, e.g., at least 2ft/min, at least 3 ft/min, at least 4 ft/min, at least 5 ft/min, atleast 10 ft/min, at least 15 ft/min, 20, 25, 30, 35, 40, 45, 50 ft/min.The rate of conveying is related to the beam current, for example, for a¼ inch thick biomass and 100 mA, the conveyor can move at about 20ft/min to provide a useful irradiation dosage, at 50 mA the conveyor canmove at about 10 ft/min to provide approximately the same irradiationdosage.

After the biomass material has been conveyed through the radiation zone,optional post-treatment processing can be done. The optionalpost-treatment processing can, for example, be a process described withrespect to the pre-irradiation processing. For example, the biomass canbe screened, heated, cooled, and/or combined with additives. Uniquely topost-irradiation, quenching of the radicals can occur, for example,quenching of radicals by the addition of fluids or gases (e.g., oxygen,nitrous oxide, ammonia, liquids), using pressure, heat, and/or theaddition of radical scavengers. For example, the biomass can be conveyedout of the enclosed conveyor and exposed to a gas (e.g., oxygen) whereit is quenched, forming carboxylated groups. In one embodiment thebiomass is exposed during irradiation to the reactive gas or fluid.Quenching of biomass that has been irradiated is described in U.S. Pat.No. 8,083,906 published Dec. 27, 2011, the entire disclosure of which isincorporate herein by reference.

If desired, one or more mechanical treatments can be used in addition toirradiation to further reduce the recalcitrance of thecarbohydrate-containing material. These processes can be applied before,during and or after irradiation.

In some cases, the mechanical treatment may include an initialpreparation of the feedstock as received, e.g., size reduction ofmaterials, such as by comminution, e.g., cutting, grinding, shearing,pulverizing or chopping. For example, in some cases, loose feedstock(e.g., recycled paper, starchy materials, or switchgrass) is prepared byshearing or shredding. Mechanical treatment may reduce the bulk densityof the carbohydrate-containing material, increase the surface area ofthe carbohydrate-containing material and/or decrease one or moredimensions of the carbohydrate-containing material.

Alternatively, or in addition, the feedstock material can be treatedwith another treatment, for example, chemical treatments, such as withan acid (HCl, H₂SO₄, H₃PO₄), a base (e.g., KOH and NaOH), a chemicaloxidant (e.g., peroxides, chlorates, ozone), irradiation, steamexplosion, pyrolysis, sonication, oxidation, chemical treatment. Thetreatments can be in any order and in any sequence and combinations. Forexample, the feedstock material can first be physically treated by oneor more treatment methods, e.g., chemical treatment including and incombination with acid hydrolysis (e.g., utilizing HCl, H₂SO₄, H₃PO₄),radiation, sonication, oxidation, pyrolysis or steam explosion, and thenmechanically treated. This sequence can be advantageous since materialstreated by one or more of the other treatments, e.g., irradiation orpyrolysis, tend to be more brittle and, therefore, it may be easier tofurther change the structure of the material by mechanical treatment. Asanother example, a feedstock material can be conveyed through ionizingradiation using a conveyor as described herein and then mechanicallytreated. Chemical treatment can remove some or all of the lignin (forexample, chemical pulping) and can partially or completely hydrolyze thematerial. The methods also can be used with pre-hydrolyzed material. Themethods also can be used with material that has not been pre hydrolyzedThe methods can be used with mixtures of hydrolyzed and non-hydrolyzedmaterials, for example, with about 50% or more non-hydrolyzed material,with about 60% or more non-hydrolyzed material, with about 70% or morenon-hydrolyzed material, with about 80% or more non-hydrolyzed materialor even with 90% or more non-hydrolyzed material.

In addition to size reduction, which can be performed initially and/orlater in processing, mechanical treatment can also be advantageous for“opening up,” “stressing,” breaking or shattering thecarbohydrate-containing materials, making the cellulose of the materialsmore susceptible to chain scission and/or disruption of crystallinestructure during the physical treatment.

Methods of mechanically treating the carbohydrate-containing materialinclude, for example, milling or grinding. Milling may be performedusing, for example, a hammer mill, ball mill, colloid mill, conical orcone mill, disk mill, edge mill, Wiley mill, grist mill or other mill.Grinding may be performed using, for example, a cutting/impact typegrinder. Some exemplary grinders include stone grinders, pin grinders,coffee grinders, and burr grinders. Grinding or milling may be provided,for example, by a reciprocating pin or other element, as is the case ina pin mill. Other mechanical treatment methods include mechanicalripping or tearing, other methods that apply pressure to the fibers, andair attrition milling. Suitable mechanical treatments further includeany other technique that continues the disruption of the internalstructure of the material that was initiated by the previous processingsteps.

Mechanical feed preparation systems can be configured to produce streamswith specific characteristics such as, for example, specific maximumsizes, specific length-to-width, or specific surface areas ratios.Physical preparation can increase the rate of reactions, improve themovement of material on a conveyor, improve the irradiation profile ofthe material, improve the radiation uniformity of the material, orreduce the processing time required by opening up the materials andmaking them more accessible to processes and/or reagents, such asreagents in a solution.

The bulk density of feedstocks can be controlled (e.g., increased). Insome situations, it can be desirable to prepare a low bulk densitymaterial, e.g., by densifying the material (e.g., densification can makeit easier and less costly to transport to another site) and thenreverting the material to a lower bulk density state (e.g., aftertransport). The material can be densified, for example, from less thanabout 0.2 g/cc to more than about 0.9 g/cc (e.g., less than about 0.3 tomore than about 0.5 g/cc, less than about 0.3 to more than about 0.9g/cc, less than about 0.5 to more than about 0.9 g/cc, less than about0.3 to more than about 0.8 g/cc, less than about 0.2 to more than about0.5 g/cc). For example, the material can be densified by the methods andequipment disclosed in U.S. Pat. No. 7,932,065 to Medoff andInternational Publication No. WO 2008/073186 (which was filed Oct. 26,2007, was published in English, and which designated the United States),the full disclosures of which are incorporated herein by reference.Densified materials can be processed by any of the methods describedherein, or any material processed by any of the methods described hereincan be subsequently densified.

In some embodiments, the material to be processed is in the form of afibrous material that includes fibers provided by shearing a fibersource. For example, the shearing can be performed with a rotary knifecutter.

For example, a fiber source, e.g., that is recalcitrant or that has hadits recalcitrance level reduced, can be sheared, e.g., in a rotary knifecutter, to provide a first fibrous material. The first fibrous materialis passed through a first screen, e.g., having an average opening sizeof 1.59 mm or less ( 1/16 inch, 0.0625 inch), provide a second fibrousmaterial. If desired, the fiber source can be cut prior to the shearing,e.g., with a shredder. For example, when a paper is used as the fibersource, the paper can be first cut into strips that are, e.g., ¼- to½-inch wide, using a shredder, e.g., a counter-rotating screw shredder,such as those manufactured by Munson (Utica, N.Y.). As an alternative toshredding, the paper can be reduced in size by cutting to a desired sizeusing a guillotine cutter. For example, the guillotine cutter can beused to cut the paper into sheets that are, e.g., 10 inches wide by 12inches long.

In some embodiments, the shearing of the fiber source and the passing ofthe resulting first fibrous material through a first screen areperformed concurrently. The shearing and the passing can also beperformed in a batch-type process.

For example, a rotary knife cutter can be used to concurrently shear thefiber source and screen the first fibrous material. A rotary knifecutter includes a hopper that can be loaded with a shredded fiber sourceprepared by shredding a fiber source.

In some implementations, the feedstock is physically treated prior tosaccharification and/or fermentation. Physical treatment processes caninclude one or more of any of those described herein, such as mechanicaltreatment, chemical treatment, irradiation, sonication, oxidation,pyrolysis or steam explosion. Treatment methods can be used incombinations of two, three, four, or even all of these technologies (inany order). When more than one treatment method is used, the methods canbe applied at the same time or at different times. Other processes thatchange a molecular structure of a biomass feedstock may also be used,alone or in combination with the processes disclosed herein.

Mechanical treatments that may be used, and the characteristics of themechanically treated carbohydrate-containing materials, are described infurther detail in U.S. Patent Pub. 2012/0100577 A1, filed Oct. 18, 2011,the full disclosure of which is hereby incorporated herein by reference.

Sonication, Pyrolysis, Oxidation, Steam Explosion, Heating

If desired, one or more sonication, pyrolysis, oxidation, heating orsteam explosion processes can be used instead of or in addition toirradiation to reduce or further reduce the recalcitrance of thecarbohydrate-containing material. For example, these processes can beapplied before, during and or after irradiation. These processes aredescribed in detail in U.S. Pat. No. 7,932,065 to Medoff, the fulldisclosure of which is incorporated herein by reference.

Alternatively, the biomass can be heated after the biomass is treated byone or more of sonication, pyrolysis, oxidation, radiation and steamexplosion processes. For example, the biomass can be heated after thebiomass is irradiated prior to a saccharification step. The heating canbe created, for example, by IR radiation, microwaves, combustion (e.g.,gas, coal, oil, and/or biomass), resistive heating and/or inductivecoils. This heating can be in a liquid, for example, in water or otherwater-based solvents. The heat can be applied from at least one side ormore than one side, can be continuous or periodic and can be for only aportion of the material or all the material. The biomass can be heatedto temperatures above about 90 deg C. in an aqueous liquid that may havean acid or a base present. For example, the aqueous biomass slurry canbe heated to between about 90 and 150 deg C. (e.g., between about105-145 deg C., between about 110 to 140 deg C., or 115-135 deg C.). Thetime that the aqueous biomass mixture is held at the targetedtemperature range is 1 to 12 hours (e.g., 1 to 6 hours, 1 to 4 hours).In some instances, the aqueous biomass mixture is alkaline and the pH isbetween 6 and 13 (e.g., 8-12, or 8-11)

Intermediates and Products

Using the processes described herein, the biomass material can beconverted to one or more products, such as energy, fuels, foods andmaterials. For example, intermediates and products such as organicacids, salts of organic acids, anhydrides, esters of organic acids andfuels, e.g., fuels for internal combustion engines or feedstocks forfuel cells can be produced. Systems and processes are described hereinthat can use as feedstock cellulosic and/or lignocellulosic materialsthat are readily available, but often can be difficult to process, e.g.,municipal waste streams and waste paper streams, such as streams thatinclude newspaper, kraft paper, corrugated paper or mixtures of these.

Specific examples of products include, but are not limited to, hydrogen,sugars (e.g., glucose, xylose, arabinose, mannose, galactose, fructose,disaccharides, oligosaccharides and polysaccharides), alcohols (e.g.,monohydric alcohols or dihydric alcohols, such as ethanol, n-propanol,isobutanol, sec-butanol, tert-butanol or n-butanol), hydrated or hydrousalcohols (e.g., containing greater than 10%, 20%, 30% or even greaterthan 40% water), biodiesel, organic acids, hydrocarbons (e.g., methane,ethane, propane, isobutene, pentane, n-hexane, biodiesel, bio-gasolineand mixtures thereof), co-products (e.g., proteins, such as cellulolyticproteins (enzymes) or single cell proteins), and mixtures of any ofthese in any combination or relative concentration, and optionally incombination with any additives (e.g., fuel additives). Other examplesinclude carboxylic acids, salts of a carboxylic acid, a mixture ofcarboxylic acids and salts of carboxylic acids and esters of carboxylicacids (e.g., methyl, ethyl and n-propyl esters), ketones (e.g.,acetone), aldehydes (e.g., acetaldehyde), alpha and beta unsaturatedacids (e.g., acrylic acid) and olefins (e.g., ethylene). Other alcoholsand alcohol derivatives include propanol, propylene glycol,1,4-butanediol, 1,3-propanediol, sugar alcohols (e.g., erythritol,glycol, glycerol, sorbitol threitol, arabitol, ribitol, mannitol,dulcitol, fucitol, iditol, isomalt, maltitol, lactitol, xylitol andother polyols), and methyl or ethyl esters of any of these alcohols.Other products include methyl acrylate, methylmethacrylate, lactic acid,citric acid, formic acid, acetic acid, propionic acid, butyric acid,succinic acid, valeric acid, caproic acid, 3-hydroxypropionic acid,palmitic acid, stearic acid, oxalic acid, malonic acid, glutaric acid,oleic acid, linoleic acid, glycolic acid, gamma-hydroxybutyric acid, andmixtures thereof, salts of any of these acids, mixtures of any of theacids and their respective salts.

Any combination of the above products with each other, and/or of theabove products with other products, which other products may be made bythe processes described herein or otherwise, may be packaged togetherand sold as products. The products may be combined, e.g., mixed, blendedor co-dissolved, or may simply be packaged or sold together.

Any of the products or combinations of products described herein may besanitized or sterilized prior to selling the products, e.g., afterpurification or isolation or even after packaging, to neutralize one ormore potentially undesirable contaminants that could be present in theproduct(s). Such sanitation can be done with electron bombardment, forexample, by at a dosage of less than about 20 Mrad, e.g., from about 0.1to 15 Mrad, from about 0.5 to 7 Mrad, or from about 1 to 3 Mrad.

The processes described herein can produce various by-product streamsuseful for generating steam and electricity to be used in other parts ofthe plant (co-generation) or sold on the open market. For example, steamgenerated from burning by-product streams can be used in a distillationprocess. As another example, electricity generated from burningby-product streams can be used to power electron beam generators used inpretreatment.

The by-products used to generate steam and electricity are derived froma number of sources throughout the process. For example, anaerobicdigestion of wastewater can produce a biogas high in methane and a smallamount of waste biomass (sludge). As another example,post-saccharification and/or post-distillate solids (e.g., unconvertedlignin, cellulose, and hemicellulose remaining from the pretreatment andprimary processes) can be used, e.g., burned, as a fuel.

Other intermediates and products, including food and pharmaceuticalproducts, are described in U.S. Patent Pub. 2010/0124583 A1, publishedMay 20, 2010, to Medoff, the full disclosure of which is herebyincorporated by reference herein.

Lignin Derived Products

The spent biomass (e.g., spent lignocellulosic material) fromlignocellulosic processing by the methods described are expected to havea high lignin content and in addition to being useful for producingenergy through combustion in a Co-Generation plant, may have uses asother valuable products. For example, the lignin can be used as capturedas a plastic, or it can be synthetically upgraded to other plastics. Insome instances, it can also be converted to lignosulfonates, which canbe utilized as binders, dispersants, emulsifiers or as sequestrants.When used as a binder, the lignin or a lignosulfonate can, e.g., beutilized in coal briquettes, in ceramics, for binding carbon black, forbinding fertilizers and herbicides, as a dust suppressant, in the makingof plywood and particle board, for binding animal feeds, as a binder forfiberglass, as a binder in linoleum paste and as a soil stabilizer.

When used as a dispersant, the lignin or lignosulfonates can be used,e.g., concrete mixes, clay and ceramics, dyes and pigments, leathertanning and in gypsum board.

When used as an emulsifier, the lignin or lignosulfonates can be used,e.g., in asphalt, pigments and dyes, pesticides and wax emulsions.

When used as a sequestrant, the lignin or lignosulfonates can be used,e.g., in micro-nutrient systems, cleaning compounds and water treatmentsystems, e.g., for boiler and cooling systems.

For energy production lignin generally has a higher energy content thanholocellulose (cellulose and hemicellulose) since it contains morecarbon than homocellulose. For example, dry lignin can have an energycontent of between about 11,000 and 12,500 BTU per pound, compared to7,000 an 8,000 BTU per pound of holocellulose. As such, lignin can bedensified and converted into briquettes and pellets for burning. Forexample, the lignin can be converted into pellets by any methoddescribed herein. For a slower burning pellet or briquette, the lignincan be crosslinked, such as applying a radiation dose of between about0.5 Mrad and 5 Mrad. Crosslinking can make a slower burning form factor.The form factor, such as a pellet or briquette, can be converted to a“synthetic coal” or charcoal by pyrolyzing in the absence of air, e.g.,at between 400 and 950° C. Prior to pyrolyzing, it can be desirable tocrosslink the lignin to maintain structural integrity.

Saccharification

In order to convert the feedstock to a form that can be readilyprocessed the glucan- or xylan-containing cellulose in the feedstock canbe hydrolyzed to low molecular weight carbohydrates, such as sugars, bya saccharifying agent, e.g., an enzyme or acid, a process referred to assaccharification. The low molecular weight carbohydrates can then beused, for example, in an existing manufacturing plant, such as a singlecell protein plant, an enzyme manufacturing plant, or a fuel plant,e.g., an ethanol manufacturing facility.

The feedstock can be hydrolyzed using an enzyme, e.g., by combining thematerials and the enzyme in a solvent, e.g., in an aqueous solution.

Alternatively, the enzymes can be supplied by organisms that break downbiomass, such as the cellulose and/or the lignin portions of thebiomass, contain or manufacture various cellulolytic enzymes(cellulases), ligninases or various small molecule biomass-degradingmetabolites. These enzymes may be a complex of enzymes that actsynergistically to degrade crystalline cellulose or the lignin portionsof biomass. Examples of cellulolytic enzymes include: endoglucanases,cellobiohydrolases, and cellobiases (beta-glucosidases).

During saccharification a cellulosic substrate can be initiallyhydrolyzed by endoglucanases at random locations producing oligomericintermediates. These intermediates are then substrates for exo-splittingglucanases such as cellobiohydrolase to produce cellobiose from the endsof the cellulose polymer. Cellobiose is a water-soluble 1,4-linked dimerof glucose. Finally, cellobiase cleaves cellobiose to yield glucose. Theefficiency (e.g., time to hydrolyze and/or completeness of hydrolysis)of this process depends on the recalcitrance of the cellulosic material.

Therefore, the treated biomass materials can be saccharified, bycombining the material and a cellulase enzyme in a fluid medium, e.g.,an aqueous solution. In some cases, the material is boiled, steeped, orcooked in hot water prior to saccharification, as described in U.S.Patent Pub. 2012/0100577 A1 by Medoff and Masterman, published on Apr.26, 2012, the entire contents of which are incorporated herein.

The saccharification process can be partially or completely performed ina tank (e.g., a tank having a volume of at least 4000, 40,000, or500,000 L) in a manufacturing plant, and/or can be partially orcompletely performed in transit, e.g., in a rail car, tanker truck, orin a supertanker or the hold of a ship. The time required for completesaccharification will depend on the process conditions and thecarbohydrate-containing material and enzyme used. If saccharification isperformed in a manufacturing plant under controlled conditions, thecellulose may be substantially entirely converted to sugar, e.g.,glucose in about 12-96 hours. If saccharification is performed partiallyor completely in transit, saccharification may take longer.

It is generally preferred that the tank contents be mixed duringsaccharification, e.g., using jet mixing as described in InternationalApp. No. PCT/US2010/035331, filed May 18, 2010, which was published inEnglish as WO 2010/135380 and designated the United States, the fulldisclosure of which is incorporated by reference herein.

The addition of surfactants can enhance the rate of saccharification.Examples of surfactants include non-ionic surfactants, such as a Tween®20 or Tween® 80 polyethylene glycol surfactants, ionic surfactants, oramphoteric surfactants.

It is generally preferred that the concentration of the sugar solutionresulting from saccharification be relatively high, e.g., greater than40%, or greater than 50, 60, 70, 80, 90 or even greater than 95% byweight. Water may be removed, e.g., by evaporation, to increase theconcentration of the sugar solution. This reduces the volume to beshipped, and also inhibits microbial growth in the solution.

Alternatively, sugar solutions of lower concentrations may be used, inwhich case it may be desirable to add an antimicrobial additive, e.g., abroad spectrum antibiotic, in a low concentration, e.g., 50 to 150 ppm.Other suitable antibiotics include amphotericin B, ampicillin,chloramphenicol, ciprofloxacin, gentamicin, hygromycin B, kanamycin,neomycin, penicillin, puromycin, streptomycin. For example,antimicrobials from Lallemand Biofuels and Distilled Spirits (Montreal,Quebec, Canada) can be used such as LACTOSIDE V™, BACTENIX® V300,BACTENIX® V300SP, ALLPEN™ SPECIAL, BACTENIX® V60, BACTENIX® V60SP,BACTENIX® V50 and/or LACTOSIDE 247™. Antibiotics will inhibit growth ofmicroorganisms during transport and storage, and can be used atappropriate concentrations, e.g., between 15 and 1000 ppm by weight,e.g., between 25 and 500 ppm, or between 50 and 150 ppm. If desired, anantibiotic can be included even if the sugar concentration is relativelyhigh. Alternatively, other additives with anti-microbial of preservativeproperties may be used. Preferably the antimicrobial additive(s) arefood-grade.

A relatively high concentration solution can be obtained by limiting theamount of water added to the carbohydrate-containing material with theenzyme. The concentration can be controlled, e.g., by controlling howmuch saccharification takes place. For example, concentration can beincreased by adding more carbohydrate-containing material to thesolution. In order to keep the sugar that is being produced in solution,a surfactant can be added, e.g., one of those discussed above.Solubility can also be increased by increasing the temperature of thesolution. For example, the solution can be maintained at a temperatureof 40-50° C., 60-80° C., or even higher.

Saccharifying Agents

Suitable cellulolytic enzymes include cellulases from species in thegenera Bacillus, Coprinus, Myceliophthora, Cephalosporium, Scytalidium,Penicillium, Aspergillus, Pseudomonas, Humicola, Fusarium, Thielavia,Acremonium, Chrysosporium and Trichoderma, especially those produced bya strain selected from the species Aspergillus (see, e.g., EP Pub. No. 0458 162), Humicola insolens (reclassified as Scytalidium thermophilum,see, e.g., U.S. Pat. No. 4,435,307), Coprinus cinereus, Fusariumoxysporum, Myceliophthora thermophila, Meripilus giganteus, Thielaviaterrestris, Acremonium sp. (including, but not limited to, A.persicinum, A. acremonium, A. brachypenium, A. dichromosporum, A.obclavatum, A. pinkertoniae, A. roseogriseum, A. incoloratum, and A.furatum). Preferred strains include Humicola insolens DSM 1800, Fusariumoxysporum DSM 2672, Myceliophthora thermophila CBS 117.65,Cephalosporium sp. RYM-202, Acremonium sp. CBS 478.94, Acremonium sp.CBS 265.95, Acremonium persicinum CBS 169.65, Acremonium acremonium AHU9519, Cephalosporium sp. CBS 535.71, Acremonium brachypenium CBS 866.73,Acremonium dichromosporum CBS 683.73, Acremonium obclavatum CBS 311.74,Acremonium pinkertoniae CBS 157.70, Acremonium roseogriseum CBS 134.56,Acremonium incoloratum CBS 146.62, and Acremonium furatum CBS 299.70H.Cellulolytic enzymes may also be obtained from Chrysosporium, preferablya strain of Chrysosporium lucknowense. Additional strains that can beused include, but are not limited to, Trichoderma (particularly T.viride, T. reesei, and T. koningii), alkalophilic Bacillus (see, forexample, U.S. Pat. No. 3,844,890 and EP Pub. No. 0 458 162), andStreptomyces (see, e.g., EP Pub. No. 0 458 162).

In addition to or in combination to enzymes, acids, bases and otherchemicals (e.g., oxidants) can be utilized to saccharify lignocellulosicand cellulosic materials. These can be used in any combination orsequence (e.g., before, after and/or during addition of an enzyme). Forexample, strong mineral acids can be utilized (e.g. HCl, H₂SO₄, H₃PO₄)and strong bases (e.g., NaOH, KOH).

Sugars

In the processes described herein, for example, after saccharification,sugars (e.g., glucose and xylose) can be isolated and/or purified. Forexample, sugars can be isolated and/or purified by precipitation,crystallization, chromatography (e.g., simulated moving bedchromatography, high pressure chromatography), electrodialysis,centrifugation, extraction, any other isolation method known in the art,and combinations thereof.

Hydrogenation and Other Chemical Transformations

The processes described herein can include hydrogenation. For example,glucose and xylose can be hydrogenated to sorbitol and xylitolrespectively. Hydrogenation can be accomplished by use of a catalyst(e.g., Pt/gamma-Al₂O₃, Ru/C, Raney Nickel, or other catalysts know inthe art) in combination with thunder high pressure (e.g., 10 to 12000psi). Other types of chemical transformation of the products from theprocesses described herein can be used, for example, production oforganic sugar derived products such (e.g., furfural and furfural-derivedproducts). Chemical transformations of sugar derived products aredescribed in U.S. Ser. No. 13/934,704 filed Jul. 3, 2013, the entiredisclosure of which is incorporated herein by reference in its entirety.

Fermentation

Yeast and Zymomonas bacteria, for example, can be used for fermentationor conversion of sugar(s) to alcohol(s). Other microorganisms arediscussed below. The optimum pH for fermentations is about pH 4 to 7.For example, the optimum pH for yeast is from about pH 4 to 5, while theoptimum pH for Zymomonas is from about pH 5 to 6. Typical fermentationtimes are about 24 to 168 hours (e.g., 24 to 96 hrs) with temperaturesin the range of 20° C. to 40° C. (e.g., 26° C. to 40° C.), however,thermophilic microorganisms prefer higher temperatures.

In some embodiments, e.g., when anaerobic organisms are used, at least aportion of the fermentation is conducted in the absence of oxygen, e.g.,under a blanket of an inert gas such as N₂, Ar, He, CO₂ or mixturesthereof. Additionally, the mixture may have a constant purge of an inertgas flowing through the tank during part of or all of the fermentation.In some cases, anaerobic condition, can be achieved or maintained bycarbon dioxide production during the fermentation and no additionalinert gas is needed.

In some embodiments, all or a portion of the fermentation process can beinterrupted before the low molecular weight sugar is completelyconverted to a product (e.g., ethanol). The intermediate fermentationproducts include sugar and carbohydrates in high concentrations. Thesugars and carbohydrates can be isolated via any means known in the art.These intermediate fermentation products can be used in preparation offood for human or animal consumption. Additionally or alternatively, theintermediate fermentation products can be ground to a fine particle sizein a stainless-steel laboratory mill to produce a flour-like substance.Jet mixing may be used during fermentation, and in some casessaccharification and fermentation are performed in the same tank.

Nutrients for the microorganisms may be added during saccharificationand/or fermentation, for example, the food-based nutrient packagesdescribed in U.S. Patent Pub. 2012/0052536, filed Jul. 15, 2011, thecomplete disclosure of which is incorporated herein by reference.

“Fermentation” includes the methods and products that are disclosed inapplications Nos. PCT/US2012/71093 published Jun. 27, 2013,PCT/US2012/71907 published Jun. 27, 2012, and PCT/US2012/71083 publishedJun. 27, 2012 the contents of which are incorporated by reference hereinin their entirety.

Mobile fermenters can be utilized, as described in International App.No. PCT/US2007/074028 (which was filed Jul. 20, 2007, was published inEnglish as WO 2008/011598 and designated the United States) and has aU.S. Pat. No. 8,318,453, the contents of which are incorporated hereinin its entirety. Similarly, the saccharification equipment can bemobile. Further, saccharification and/or fermentation may be performedin part or entirely during transit.

Fermentation Agents

The microorganism(s) used in fermentation can be naturally-occurringmicroorganisms and/or engineered microorganisms. For example, themicroorganism can be a bacterium (including, but not limited to, e.g., acellulolytic bacterium), a fungus, (including, but not limited to, e.g.,a yeast), a plant, a protist, e.g., a protozoa or a fungus-like protest(including, but not limited to, e.g., a slime mold), or an alga. Whenthe organisms are compatible, mixtures of organisms can be utilized.

Suitable fermenting microorganisms have the ability to convertcarbohydrates, such as glucose, fructose, xylose, arabinose, mannose,galactose, oligosaccharides or polysaccharides into fermentationproducts. Fermenting microorganisms include strains of the genusSaccharomyces spp. (including, but not limited to, S. cerevisiae(baker's yeast), S. distaticus, S. uvarum), the genus Kluyveromyces,(including, but not limited to, K. marxianus, K. fragilis), the genusCandida (including, but not limited to, C. pseudotropicalis, and C.brassicae), Pichia stipitis (a relative of Candida shehatae), the genusClavispora (including, but not limited to, C. lusitaniae and C.opuntiae), the genus Pachysolen (including, but not limited to, P.tannophilus), the genus Bretannomyces (including, but not limited to,e.g., B. clausenii (Philippidis, G. P., 1996, Cellulose bioconversiontechnology, in Handbook on Bioethanol: Production and Utilization,Wyman, C. E., ed., Taylor & Francis, Washington, D.C., 179-212)). Othersuitable microorganisms include, for example, Zymomonas mobilis,Clostridium spp. (including, but not limited to, C. thermocellum(Philippidis, 1996, supra), C. saccharobutylacetonicum, C. tyrobutyricumC. saccharobutylicum, C. Puniceum, C. beijernckii, and C.acetobutylicum), Moniliella spp. (including but not limited to M.pollinis, M. tomentosa, M. madida, M. nigrescens, M. oedocephali, M.megachiliensis), Yarrowia lipolytica, Aureobasidium sp.,Trichosporonoides sp., Trigonopsis variabilis, Trichosporon sp.,Moniliellaacetoabutans sp., Typhula variabilis, Candida magnoliae,Ustilaginomycetes sp., Pseudozyma tsukubaensis, yeast species of generaZygosaccharomyces, Debaryomyces, Hansenula and Pichia, and fungi of thedematioid genus Torula (e.g., T. corallina).

Many such microbial strains are publicly available, either commerciallyor through depositories such as the ATCC (American Type CultureCollection, Manassas, Va., USA), the NRRL (Agricultural Research ServiceCulture Collection, Peoria, Ill., USA), or the DSMZ (Deutsche Sammlungvon Mikroorganismen and Zellkulturen GmbH, Braunschweig, Germany), toname a few.

Commercially available yeasts include, for example, RED STAR®/LesaffreEthanol Red (available from Red Star/Lesaffre, USA), FALI® (availablefrom Fleischmann's Yeast, a division of Burns Philip Food Inc., USA),SUPERSTART® (Lallemand Biofuels and Distilled Spirits, Canada), EAGLE C6FUEL™ or C6 FUEL™ (available from Lallemand Biofuels and DistilledSpirits, Canada), (GERT STRAND® (available from Gert Strand AB, Sweden),and FERMOL® (available from DSM Specialties).

Distillation

After fermentation, the resulting fluids can be distilled using, forexample, a “beer column” to separate ethanol and other alcohols from themajority of water and residual solids. The vapor exiting the beer columncan be, e.g., 35% by weight ethanol and can be fed to a rectificationcolumn. A mixture of nearly azeotropic (92.5%) ethanol and water fromthe rectification column can be purified to pure (99.5%) ethanol usingvapor-phase molecular sieves. The beer column bottoms can be sent to thefirst effect of a three-effect evaporator. The rectification columnreflux condenser can provide heat for this first effect. After the firsteffect, solids can be separated using a centrifuge and dried in a rotarydryer. A portion (25%) of the centrifuge effluent can be recycled tofermentation and the rest sent to the second and third evaporatoreffects. Most of the evaporator condensate can be returned to theprocess as fairly clean condensate with a small portion split off towaste water treatment to prevent build-up of low-boiling compounds.

Hydrocarbon-Containing Materials

In other embodiments utilizing the methods and systems described herein,hydrocarbon-containing materials can be processed. Any process describedherein can be used to treat any hydrocarbon-containing material hereindescribed. “Hydrocarbon-containing materials,” as used herein, is meantto include oil sands, oil shale, tar sands, coal dust, coal slurry,bitumen, various types of coal, and other naturally-occurring andsynthetic materials that include both hydrocarbon components and solidmatter. The solid matter can include rock, sand, clay, stone, silt,drilling slurry, or other solid organic and/or inorganic matter. Theterm can also include waste products such as drilling waste andby-products, refining waste and by-products, or other waste productscontaining hydrocarbon components, such as asphalt shingling andcovering, asphalt pavement, etc.

In yet other embodiments utilizing the methods and systems describedherein, wood and wood containing produces can be processed. For example,lumber products can be processed, e.g. boards, sheets, laminates, beams,particle boards, composites, rough cut wood, soft wood and hard wood. Inaddition, cut trees, bushes, wood chips, saw dust, roots, bark, stumps,decomposed wood and other wood containing biomass material can beprocessed.

Conveying Systems

Various conveying systems, including and in addition to the conveyingsystems already discussed herein can be used to convey the biomassmaterial, for example, as discussed, to a vault, and under an electronbeam in a vault. Exemplary conveyors are belt conveyors, pneumaticconveyors, screw conveyors, carts, trains, trains or carts on rails,elevators, front loaders, backhoes, cranes, various scrapers andshovels, trucks, and throwing devices can be used.

Optionally, including and in addition to the conveying systems describedherein, one or more other conveying systems can be enclosed. When usingan enclosure, the enclosed conveyor can also be purged with an inert gasso as to maintain an atmosphere at a reduced oxygen level. Keepingoxygen levels low avoids the formation of ozone which in some instancesis undesirable due to its reactive and toxic nature. For example, theoxygen can be less than about 20% (e.g., less than about 10%, less thanabout 1%, less than about 0.1%, less than about 0.01%, or even less thanabout 0.001% oxygen). Purging can be done with an inert gas including,but not limited to, nitrogen, argon, helium or carbon dioxide. This canbe supplied, for example, from a boil off of a liquid source (e.g.,liquid nitrogen or helium), generated or separated from air in situ, orsupplied from tanks. The inert gas can be recirculated and any residualoxygen can be removed using a catalyst, such as a copper catalyst bed.Alternatively, combinations of purging, recirculating and oxygen removalcan be done to keep the oxygen levels low.

The enclosed conveyor can also be purged with a reactive gas that canreact with the biomass. This can be done before, during or after theirradiation process. The reactive gas can be, but is not limited to,nitrous oxide, ammonia, oxygen, ozone, hydrocarbons, aromatic compounds,amides, peroxides, azides, halides, oxyhalides, phosphides, phosphines,arsines, sulfides, thiols, boranes and/or hydrides. The reactive gas canbe activated in the enclosure, e.g., by irradiation (e.g., electronbeam, UV irradiation, microwave irradiation, heating, IR radiation), sothat it reacts with the biomass. The biomass itself can be activated,for example, by irradiation. Preferably the biomass is activated by theelectron beam, to produce radicals which then react with the activatedor unactivated reactive gas, e.g., by radical coupling or quenching.Purging gases supplied to an enclosed conveyor can also be cooled, forexample, below about 25° C., below about 0° C., below about −40° C.,below about −80° C., below about −120° C. For example, the gas can beboiled off from a compressed gas such as liquid nitrogen or sublimedfrom solid carbon dioxide. As an alternative example, the gas can becooled by a chiller or part of or the entire conveyor can be cooled.

Other Embodiments

Any material, processes or processed materials discussed herein can beused to make products and/or intermediates such as composites, fillers,binders, plastic additives, adsorbents and controlled release agents.The methods can include densification, for example, by applying pressureand heat to the materials. For example, composites can be made bycombining fibrous materials with a resin or polymer. For example,radiation cross-linkable resin, e.g., a thermoplastic resin can becombined with a fibrous material to provide a fibrousmaterial/cross-linkable resin combination. Such materials can be, forexample, useful as building materials, protective sheets, containers andother structural materials (e.g., molded and/or extruded products).Absorbents can be, for example, in the form of pellets, chips, fibersand/or sheets. Adsorbents can be used, for example, as pet bedding,packaging material or in pollution control systems. Controlled releasematrices can also be the form of, for example, pellets, chips, fibersand or sheets. The controlled release matrices can, for example, be usedto release drugs, biocides, fragrances. For example, composites,absorbents and control release agents and their uses are described inInternational Application No. PCT/US2006/010648, filed Mar. 23, 2006,and U.S. Pat. No. 8,074,910 filed Nov. 22, 2011, the entire disclosuresof which are herein incorporated by reference.

In some instances the biomass material is treated at a first level toreduce recalcitrance, e.g., utilizing accelerated electrons, toselectively release one or more sugars (e.g., xylose). The biomass canthen be treated to a second level to release one or more other sugars(e.g., glucose). Optionally the biomass can be dried between treatments.The treatments can include applying chemical and biochemical treatmentsto release the sugars. For example, a biomass material can be treated toa level of less than about 20 Mrad (e.g., less than about 15 Mrad, lessthan about 10 Mrad, less than about 5 Mrad, less than about 2 Mrad) andthen treated with a solution of sulfuric acid, containing less than 10%sulfuric acid (e.g., less than about 9%, less than about 8%, less thanabout 7%, less than about 6%, less than about 5%, less than about 4%,less than about 3%, less than about 2%, less than about 1%, less thanabout 0.75%, less than about 0.50%, less than about 0.25%) to releasexylose. Xylose, for example, that is released into solution, can beseparated from solids and optionally the solids washed with asolvent/solution (e.g., with water and/or acidified water). Optionally,the solids can be dried, for example, in air and/or under vacuumoptionally with heating (e.g., below about 150 deg C., below about 120deg C.) to a water content below about 25 wt % (below about 20 wt. %,below about 15 wt. %, below about 10 wt. %, below about 5 wt. %). Thesolids can then be treated with a level of less than about 30 Mrad(e.g., less than about 25 Mrad, less than about 20 Mrad, less than about15 Mrad, less than about 10 Mrad, less than about 5 Mrad, less thanabout 1 Mrad or even not at all) and then treated with an enzyme (e.g.,a cellulase) to release glucose. The glucose (e.g., glucose in solution)can be separated from the remaining solids. The solids can then befurther processed, for example, utilized to make energy or otherproducts (e.g., lignin derived products).

Flavors, Fragrances and Colorants

Any of the products and/or intermediates described herein, for example,produced by the processes, systems and/or equipment described herein,can be combined with flavors, fragrances, colorants and/or mixtures ofthese. For example, any one or more of (optionally along with flavors,fragrances and/or colorants) sugars, organic acids, fuels, polyols, suchas sugar alcohols, biomass, fibers and composites can be combined with(e.g., formulated, mixed or reacted) or used to make other products. Forexample, one or more such product can be used to make soaps, detergents,candies, drinks (e.g., cola, wine, beer, liquors such as gin or vodka,sports drinks, coffees, teas), pharmaceuticals, adhesives, sheets (e.g.,woven, none woven, filters, tissues) and/or composites (e.g., boards).For example, one or more such product can be combined with herbs,flowers, petals, spices, vitamins, potpourri, or candles. For example,the formulated, mixed or reacted combinations can haveflavors/fragrances of grapefruit, orange, apple, raspberry, banana,lettuce, celery, cinnamon, chocolate, vanilla, peppermint, mint, onion,garlic, pepper, saffron, ginger, milk, wine, beer, tea, lean beef, fish,clams, olive oil, coconut fat, pork fat, butter fat, beef bouillon,legume, potatoes, marmalade, ham, coffee and cheeses.

Flavors, fragrances and colorants can be added in any amount, such asbetween about 0.001 wt. % to about 30 wt. %, e.g., between about 0.01 toabout 20, between about 0.05 to about 10, or between about 0.1 wt. % toabout 5 wt. %. These can be formulated, mixed and or reacted (e.g., withany one of more product or intermediate described herein) by any meansand in any order or sequence (e.g., agitated, mixed, emulsified, gelled,infused, heated, sonicated, and/or suspended). Fillers, binders,emulsifier, antioxidants can also be utilized, for example, proteingels, starches and silica.

In one embodiment the flavors, fragrances and colorants can be added tothe biomass immediately after the biomass is irradiated such that thereactive sites created by the irradiation may react with reactivecompatible sites of the flavors, fragrances, and colorants.

The flavors, fragrances and colorants can be natural and/or syntheticmaterials. These materials can be one or more of a compound, acomposition or mixtures of these (e.g., a formulated or naturalcomposition of several compounds). Optionally the flavors, fragrances,antioxidants and colorants can be derived biologically, for example,from a fermentation process (e.g., fermentation of saccharifiedmaterials as described herein). Alternatively, or additionally theseflavors, fragrances and colorants can be harvested from a whole organism(e.g., plant, fungus, animal, bacteria or yeast) or a part of anorganism. The organism can be collected and or extracted to providecolor, flavors, fragrances and/or antioxidant by any means includingutilizing the methods, systems and equipment described herein, hot waterextraction, supercritical fluid extraction, chemical extraction (e.g.,solvent or reactive extraction including acids and bases), mechanicalextraction (e.g., pressing, comminuting, filtering), utilizing anenzyme, utilizing a bacteria such as to break down a starting material,and combinations of these methods. The compounds can be derived by achemical reaction, for example, the combination of a sugar (e.g., asproduced as described herein) with an amino acid (Maillard reaction).The flavor, fragrance, antioxidant and/or colorant can be anintermediate and or product produced by the methods, equipment orsystems described herein, for example, and ester and a lignin derivedproduct.

Some examples of flavor, fragrances or colorants are polyphenols.Polyphenols are pigments responsible for the red, purple and bluecolorants of many fruits, vegetables, cereal grains, and flowers.Polyphenols also can have antioxidant properties and often have a bittertaste. The antioxidant properties make these important preservatives. Onclass of polyphenols are the flavonoids, such as Anthocyanidines,flavanonols, flavan-3-ols, s, flavanones and flavanonols. Other phenoliccompounds that can be used include phenolic acids and their esters, suchas chlorogenic acid and polymeric tannins.

Among the colorants inorganic compounds, minerals or organic compoundscan be used, for example, titanium dioxide, zinc oxide, aluminum oxide,cadmium yellow (E.g., CdS), cadmium orange (e.g., CdS with some Se),alizarin crimson (e.g., synthetic or non-synthetic rose madder),ultramarine (e.g., synthetic ultramarine, natural ultramarine, syntheticultramarine violet), cobalt blue, cobalt yellow, cobalt green, viridian(e.g., hydrated chromium(III)oxide), chalcophylite, conichalcite,cornubite, cornwallite and liroconite. Black pigments such as carbonblack and self-dispersed blacks may be used.

Some flavors and fragrances that can be utilized include ACALEA TBHQ,ACET C-6, ALLYL AMYL GLYCOLATE, ALPHA TERPINEOL, AMBRETTOLIDE, AMBRINOL95, ANDRANE, APHERMATE, APPLELIDE, BACDANOL®, BERGAMAL, BETA IONONEEPDXIDE, BETA NAPHTHYL ISO-BUTYL ETHER, BICYCLONONALACTONE, BORNAFIX®,CANTHOXAL, CASHMERAN®, CASHMERAN® VELVET, CASSIFFIX®, CEDRAFIX,CEDRAMBER®, CEDRYL ACETATE, CELESTOLIDE, CINNAMALVA, CITRAL DIMETHYLACETATE, CITROLATE™, CITRONELLOL 700, CITRONELLOL 950, CITRONELLOLCOEUR, CITRONELLYL ACETATE, CITRONELLYL ACETATE PURE, CITRONELLYLFORMATE, CLARYCET, CLONAL, CONIFERAN, CONIFERAN PURE, CORTEX ALDEHYDE50% PEOMOSA, CYCLABUTE, CYCLACET®, CYCLAPROP®, CYCLEMAX™, CYCLOHEXYLETHYL ACETATE, DAMASCOL, DELTA DAMASCONE, DIHYDRO CYCLACET, DIHYDROMYRCENOL, DIHYDRO TERPINEOL, DIHYDRO TERPINYL ACETATE, DIMETHYLCYCLORMOL, DIMETHYL OCTANOL PQ, DIMYRCETOL, DIOLA, DIPENTENE, DULCINYL®RECRYSTALLIZED, ETHYL-3-PHENYL GLYCIDATE, FLEURAMONE, FLEURANIL, FLORALSUPER, FLORALOZONE, FLORIFFOL, FRAISTONE, FRUCTONE, GALAXOLIDE® 50,GALAXOLIDE® 50 BB, GALAXOLIDE® 50 IPM, GALAXOLIDE® UNDILUTED,GALBASCONE, GERALDEHYDE, GERANIOL 5020, GERANIOL 600 TYPE, GERANIOL 950,GERANIOL 980 (PURE), GERANIOL CFT COEUR, GERANIOL COEUR, GERANYL ACETATECOEUR, GERANYL ACETATE, PURE, GERANYL FORMATE, GRISALVA, GUAIYL ACETATE,HELIONAL™, HERBAC, HERBALIME™, HEXADECANOLIDE, HEXALON, HEXENYLSALICYLATE CIS 3-, HYACINTH BODY, HYACINTH BODY NO. 3, HYDRATROPICALDEHYDE.DMA, HYDROXYOL, INDOLAROME, INTRELEVEN ALDEHYDE, INTRELEVENALDEHYDE SPECIAL, IONONE ALPHA, IONONE BETA, ISO CYCLO CITRAL, ISO CYCLOGERANIOL, ISO E SUPER®, ISOBUTYL QUINOLINE, JASMAL, JESSEMAL®,KHARISMAL®, KHARISMAL® SUPER, KHUSINIL, KOAVONE®, KOHINOOL®, LIFFAROME™,LIMOXAL, LINDENOL™, LYRAL®, LYRAME SUPER, MANDARIN ALD 10% TRI ETH,CITR, MARITIMA, MCK CHINESE, MEIJIFF™, MELAFLEUR, MELOZONE, METHYLANTHRANILATE, METHYL IONONE ALPHA EXTRA, METHYL IONONE GAMMA A, METHYLIONONE GAMMA COEUR, METHYL IONONE GAMMA PURE, METHYL LAVENDER KETONE,MONTAVERDI®, MUGUESIA, MUGUET ALDEHYDE 50, MUSK Z4, MYRAC ALDEHYDE,MYRCENYL ACETATE, NECTARATE™, NEROL 900, NERYL ACETATE, OCIMENE,OCTACETAL, ORANGE FLOWER ETHER, ORIVONE, ORRINIFF 25%, OXASPIRANE,OZOFLEUR, PAMPLEFLEUR®, PEOMOSA, PHENOXANOL®, PICONIA, PRECYCLEMONE B,PRENYL ACETATE, PRISMANTOL, RESEDA BODY, ROSALVA, ROSAMUSK, SANJINOL,SANTALIFF™, SYVERTAL, TERPINEOL, TERPINOLENE 20, TERPINOLENE 90 PQ,TERPINOLENE RECT., TERPINYL ACETATE, TERPINYL ACETATE JAX, TETRAHYDRO,MUGUOL®, TETRAHYDRO MYRCENOL, TETRAMERAN, TIMBERSILK™, TOBACAROL,TRIMOFIX® 0 TT, TRIPLAL®, TRISAMBER®, VANORIS, VERDOX™, VERDOX™ HC,VERTENEX®, VERTENEX® HC, VERTOFIX® COEUR, VERTOLIFF, VERTOLIFF ISO,VIOLIFF, VIVALDIE, ZENOLIDE, ABS INDIA 75 PCT MIGLYOL, ABS MOROCCO 50PCT DPG, ABS MOROCCO 50 PCT TEC, ABSOLUTE FRENCH, ABSOLUTE INDIA,ABSOLUTE MD 50 PCT BB, ABSOLUTE MOROCCO, CONCENTRATE PG, TINCTURE 20PCT, AMBERGRIS, AMBRETTE ABSOLUTE, AMBRETTE SEED OIL, ARMOISE OIL 70 PCTTHUYONE, BASIL ABSOLUTE GRAND VERT, BASIL GRAND VERT ABS MD, BASIL OILGRAND VERT, BASIL OIL VERVEINA, BASIL OIL VIETNAM, BAY OIL TERPENELESS,BEESWAX ABS N G, BEESWAX ABSOLUTE, BENZOIN RESINOID SIAM, BENZOINRESINOID SIAM 50 PCT DPG, BENZOIN RESINOID SIAM 50 PCT PG, BENZOINRESINOID SIAM 70.5 PCT TEC, BLACKCURRANT BUD ABS 65 PCT PG, BLACKCURRANTBUD ABS MD 37 PCT TEC, BLACKCURRANT BUD ABS MIGLYOL, BLACKCURRANT BUDABSOLUTE BURGUNDY, BOIS DE ROSE OIL, BRAN ABSOLUTE, BRAN RESINOID, BROOMABSOLUTE ITALY, CARDAMOM GUATEMALA CO2 EXTRACT, CARDAMOM OIL GUATEMALA,CARDAMOM OIL INDIA, CARROT HEART, CASSIE ABSOLUTE EGYPT, CASSIE ABSOLUTEMD 50 PCT IPM, CASTOREUM ABS 90 PCT TEC, CASTOREUM ABS C 50 PCT MIGLYOL,CASTOREUM ABSOLUTE, CASTOREUM RESINOID, CASTOREUM RESINOID 50 PCT DPG,CEDROL CEDRENE, CEDRUS ATLANTICA OIL REDIST, CHAMOMILE OIL ROMAN,CHAMOMILE OIL WILD, CHAMOMILE OIL WILD LOW LIMONENE, CINNAMON BARK OILCEYLAN, CISTE ABSOLUTE, CISTE ABSOLUTE COLORLESS, CITRONELLA OIL ASIAIRON FREE, CIVET ABS 75 PCT PG, CIVET ABSOLUTE, CIVET TINCTURE 10 PCT,CLARY SAGE ABS FRENCH DECOL, CLARY SAGE ABSOLUTE FRENCH, CLARY SAGEC′LESS 50 PCT PG, CLARY SAGE OIL FRENCH, COPAIBA BALSAM, COPAIBA BALSAMOIL, CORIANDER SEED OIL, CYPRESS OIL, CYPRESS OIL ORGANIC, DAVANA OIL,GALBANOL, GALBANUM ABSOLUTE COLORLESS, GALBANUM OIL, GALBANUM RESINOID,GALBANUM RESINOID 50 PCT DPG, GALBANUM RESINOID HERCOLYN BHT, GALBANUMRESINOID TEC BHT, GENTIANE ABSOLUTE MD 20 PCT BB, GENTIANE CONCRETE,GERANIUM ABS EGYPT MD, GERANIUM ABSOLUTE EGYPT, GERANIUM OIL CHINA,GERANIUM OIL EGYPT, GINGER OIL 624, GINGER OIL RECTIFIED SOLUBLE,GUAIACWOOD HEART, HAY ABS MD 50 PCT BB, HAY ABSOLUTE, HAY ABSOLUTE MD 50PCT TEC, HEALINGWOOD, HYSSOP OIL ORGANIC, IMMORTELLE ABS YUGO MD 50 PCTTEC, IMMORTELLE ABSOLUTE SPAIN, IMMORTELLE ABSOLUTE YUGO, JASMIN ABSINDIA MD, JASMIN ABSOLUTE EGYPT, JASMIN ABSOLUTE INDIA, ASMIN ABSOLUTEMOROCCO, JASMIN ABSOLUTE SAMBAC, JONQUILLE ABS MD 20 PCT BB, JONQUILLEABSOLUTE France, JUNIPER BERRY OIL FLG, JUNIPER BERRY OIL RECTIFIEDSOLUBLE, LABDANUM RESINOID 50 PCT TEC, LABDANUM RESINOID BB, LABDANUMRESINOID MD, LABDANUM RESINOID MD 50 PCT BB, LAVANDIN ABSOLUTE H,LAVANDIN ABSOLUTE MD, LAVANDIN OIL ABRIAL ORGANIC, LAVANDIN OIL GROSSOORGANIC, LAVANDIN OIL SUPER, LAVENDER ABSOLUTE H, LAVENDER ABSOLUTE MD,LAVENDER OIL COUMARIN FREE, LAVENDER OIL COUMARIN FREE ORGANIC, LAVENDEROIL MAILLETTE ORGANIC, LAVENDER OIL MT, MACE ABSOLUTE BB, MAGNOLIAFLOWER OIL LOW METHYL EUGENOL, MAGNOLIA FLOWER OIL, MAGNOLIA FLOWER OILMD, MAGNOLIA LEAF OIL, MANDARIN OIL MD, MANDARIN OIL MD BHT, MATEABSOLUTE BB, MOSS TREE ABSOLUTE MD TEX IFRA 43, MOSS-OAK ABS MD TEC IFRA43, MOSS-OAK ABSOLUTE IFRA 43, MOSS-TREE ABSOLUTE MD IPM IFRA 43, MYRRHRESINOID BB, MYRRH RESINOID MD, MYRRH RESINOID TEC, MYRTLE OIL IRONFREE, MYRTLE OIL TUNISIA RECTIFIED, NARCISSE ABS MD 20 PCT BB, NARCISSEABSOLUTE FRENCH, NEROLI OIL TUNISIA, NUTMEG OIL TERPENELESS, OEILLETABSOLUTE, OLIBANUM RESINOID, OLIBANUM RESINOID BB, OLIBANUM RESINOIDDPG, OLIBANUM RESINOID EXTRA 50 PCT DPG, OLIBANUM RESINOID MD, OLIBANUMRESINOID MD 50 PCT DPG, OLIBANUM RESINOID TEC, OPOPONAX RESINOID TEC,ORANGE BIGARADE OIL MD BHT, ORANGE BIGARADE OIL MD SCFC, ORANGE FLOWERABSOLUTE TUNISIA, ORANGE FLOWER WATER ABSOLUTE TUNISIA, ORANGE LEAFABSOLUTE, ORANGE LEAF WATER ABSOLUTE TUNISIA, ORRIS ABSOLUTE ITALY,ORRIS CONCRETE 15 PCT IRONE, ORRIS CONCRETE 8 PCT IRONE, ORRIS NATURAL15 PCT IRONE 4095C, ORRIS NATURAL 8 PCT IRONE 2942C, ORRIS RESINOID,OSMANTHUS ABSOLUTE, OSMANTHUS ABSOLUTE MD 50 PCT BB, PATCHOULI HEART No3, PATCHOULI OIL INDONESIA, PATCHOULI OIL INDONESIA IRON FREE, PATCHOULIOIL INDONESIA MD, PATCHOULI OIL REDIST, PENNYROYAL HEART, PEPPERMINTABSOLUTE MD, PETITGRAIN BIGARADE OIL TUNISIA, PETITGRAIN CITRONNIER OIL,PETITGRAIN OIL PARAGUAY TERPENELESS, PETITGRAIN OIL TERPENELESS STAB,PIMENTO BERRY OIL, PIMENTO LEAF OIL, RHODINOL EX GERANIUM CHINA, ROSEABS BULGARIAN LOW METHYL EUGENOL, ROSE ABS MOROCCO LOW METHYL EUGENOL,ROSE ABS TURKISH LOW METHYL EUGENOL, ROSE ABSOLUTE, ROSE ABSOLUTEBULGARIAN, ROSE ABSOLUTE DAMASCENA, ROSE ABSOLUTE MD, ROSE ABSOLUTEMOROCCO, ROSE ABSOLUTE TURKISH, ROSE OIL BULGARIAN, ROSE OIL DAMASCENALOW METHYL EUGENOL, ROSE OIL TURKISH, ROSEMARY OIL CAMPHOR ORGANIC,ROSEMARY OIL TUNISIA, SANDALWOOD OIL INDIA, SANDALWOOD OIL INDIARECTIFIED, SANTALOL, SCHINUS MOLLE OIL, ST JOHN BREAD TINCTURE 10 PCT,STYRAX RESINOID, STYRAX RESINOID, TAGETE OIL, TEA TREE HEART, TONKA BEANABS 50 PCT SOLVENTS, TONKA BEAN ABSOLUTE, TUBEROSE ABSOLUTE INDIA,VETIVER HEART EXTRA, VETIVER OIL HAITI, VETIVER OIL HAITI MD, VETIVEROIL JAVA, VETIVER OIL JAVA MD, VIOLET LEAF ABSOLUTE EGYPT, VIOLET LEAFABSOLUTE EGYPT DECOL, VIOLET LEAF ABSOLUTE FRENCH, VIOLET LEAF ABSOLUTEMD 50 PCT BB, WORMWOOD OIL TERPENELESS, YLANG EXTRA OIL, YLANG III OILand combinations of these.

The colorants can be among those listed in the Colour IndexInternational by the Society of Dyers and Colourists. Colorants includedyes and pigments and include those commonly used for coloring textiles,paints, inks and inkjet inks. Some colorants that can be utilizedinclude carotenoids, arylide yellows, diarylide yellows, ß-naphthols,naphthols, benzimidazolones, disazo condensation pigments, pyrazolones,nickel azo yellow, phthalocyanines, quinacridones, perylenes andperinones, isoindolinone and isoindoline pigments, triarylcarboniumpigments, diketopyrrolo-pyrrole pigments, thioindigoids. Cartenoidsinclude, e.g., alpha-carotene, beta-carotene, gamma-carotene, lycopene,lutein and astaxanthin Annatto extract, Dehydrated beets (beet powder),Canthaxanthin, Caramel, β-Apo-8′-carotenal, Cochineal extract, Carmine,Sodium copper chlorophyllin, Toasted partially defatted cookedcottonseed flour, Ferrous gluconate, Ferrous lactate, Grape colorextract, Grape skin extract (enocianina), Carrot oil, Paprika, Paprikaoleoresin, Mica-based pearlescent pigments, Riboflavin, Saffron,Titanium dioxide, Tomato lycopene extract; tomato lycopene concentrate,Turmeric, Turmeric oleoresin, FD&C Blue No. 1, FD&C Blue No. 2, FD&CGreen No. 3, Orange B, Citrus Red No. 2, FD&C Red No. 3, FD&C Red No.40, FD&C Yellow No. 5, FD&C Yellow No. 6, Alumina (dried aluminumhydroxide), Calcium carbonate, Potassium sodium copper chlorophyllin(chlorophyllin-copper complex), Dihydroxyacetone, Bismuth oxychloride,Ferric ammonium ferrocyanide, Ferric ferrocyanide, Chromium hydroxidegreen, Chromium oxide greens, Guanine, Pyrophyllite, Talc, Aluminumpowder, Bronze powder, Copper powder, Zinc oxide, D&C Blue No. 4, D&CGreen No. 5, D&C Green No. 6, D&C Green No. 8, D&C Orange No. 4, D&COrange No. 5, D&C Orange No. 10, D&C Orange No. 11, FD&C Red No. 4, D&CRed No. 6, D&C Red No. 7, D&C Red No. 17, D&C Red No. 21, D&C Red No.22, D&C Red No. 27, D&C Red No. 28, D&C Red No. 30, D&C Red No. 31, D&CRed No. 33, D&C Red No. 34, D&C Red No. 36, D&C Red No. 39, D&C VioletNo. 2, D&C Yellow No. 7, Ext. D&C Yellow No. 7, D&C Yellow No. 8, D&CYellow No. 10, D&C Yellow No. 11, D&C Black No. 2, D&C Black No. 3 (3),D&C Brown No. 1, Ext. D&C, Chromium-cobalt-aluminum oxide, Ferricammonium citrate, Pyrogallol, Logwood extract,1,4-Bis[(2-hydroxy-ethyl)amino]-9,10-anthracenedionebis(2-propenoic)ester copolymers,1,4-Bis[(2-methylphenyl)amino]-9,10-anthracenedione,1,4-Bis[4-(2-methacryloxyethyl) phenylamino] anthraquinone copolymers,Carbazole violet, Chlorophyllin-copper complex, Chromium-cobalt-aluminumoxide, C.I. Vat Orange 1, 2-[[2,5-Diethoxy-4-[(4-methylphenyl)thiol]phenyl]azo]-1,3,5-benzenetriol, 16,23-Dihydrodinaphtho[2,3-a:2′,3′-i]naphth [2′,3′:6,7] indolo [2,3-c] carbazole-5,10,15,17,22,24-hexone,N,N′-(9,10-Dihydro-9,10-dioxo-1,5-anthracenediyl) bisbenzamide,7,16-Dichloro-6,15-dihydro-5,9,14,18-anthrazinetetrone,16,17-Dimethoxydinaphtho (1,2,3-cd:3′,2′,1′-lm) perylene-5,10-dione,Poly(hydroxyethyl methacrylate)-dye copolymers(3), Reactive Black 5,Reactive Blue 21, Reactive Orange 78, Reactive Yellow 15, Reactive BlueNo. 19, Reactive Blue No. 4, C.I. Reactive Red 11, C.I. Reactive Yellow86, C.I. Reactive Blue 163, C.I. Reactive Red 180,4-[(2,4-dimethylphenyl)azo]-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-one(solvent Yellow 18), 6-Ethoxy-2-(6-ethoxy-3-oxobenzo[b]thien-2(3H)-ylidene) benzo[b]thiophen-3(2H)-one, Phthalocyanine green,Vinyl alcohol/methyl methacrylate-dye reaction products, C.I. ReactiveRed 180, C.I. Reactive Black 5, C.I. Reactive Orange 78, C.I. ReactiveYellow 15, C.I. Reactive Blue 21, Disodium1-amino-4-[[4-[(2-bromo-1-oxoallyl)amino]-2-sulphonatophenyl]amino]-9,10-dihydro-9,10-dioxoanthracene-2-sulphonate(Reactive Blue 69), D&C Blue No. 9, [Phthalocyaninato(2-)] copper andmixtures of these.

Other than in the examples herein, or unless otherwise expresslyspecified, all of the numerical ranges, amounts, values and percentages,such as those for amounts of materials, elemental contents, times andtemperatures of reaction, ratios of amounts, and others, in thefollowing portion of the specification and attached claims may be readas if prefaced by the word “about” even though the term “about” may notexpressly appear with the value, amount, or range. Accordingly, unlessindicated to the contrary, the numerical parameters set forth in thefollowing specification and attached claims are approximations that mayvary depending upon the desired properties sought to be obtained by thepresent invention. At the very least, and not as an attempt to limit theapplication of the doctrine of equivalents to the scope of the claims,each numerical parameter should at least be construed in light of thenumber of reported significant digits and by applying ordinary roundingtechniques.

Notwithstanding that the numerical ranges and parameters setting forththe broad scope of the invention are approximations, the numericalvalues set forth in the specific examples are reported as precisely aspossible. Any numerical value, however, inherently contains errornecessarily resulting from the standard deviation found in itsunderlying respective testing measurements. Furthermore, when numericalranges are set forth herein, these ranges are inclusive of the recitedrange end points (e.g., end points may be used). When percentages byweight are used herein, the numerical values reported are relative tothe total weight.

Also, it should be understood that any numerical range recited herein isintended to include all sub-ranges subsumed therein. For example, arange of “1 to 10” is intended to include all sub-ranges between (andincluding) the recited minimum value of 1 and the recited maximum valueof 10, that is, having a minimum value equal to or greater than 1 and amaximum value of equal to or less than 10. The terms “one,” “a,” or “an”as used herein are intended to include “at least one” or “one or more,”unless otherwise indicated. Any patent, publication, or other disclosurematerial, in whole or in part, that is said to be incorporated byreference herein is incorporated herein only to the extent that theincorporated material does not conflict with existing definitions,statements, or other disclosure material set forth in this disclosure.As such, and to the extent necessary, the disclosure as explicitly setforth herein supersedes any conflicting material incorporated herein byreference. Any material, or portion thereof, that is said to beincorporated by reference herein, but which conflicts with existingdefinitions, statements, or other disclosure material set forth hereinwill only be incorporated to the extent that no conflict arises betweenthat incorporated material and the existing disclosure material.

While this invention has been particularly shown and described withreferences to preferred embodiments thereof, it will be understood bythose skilled in the art that various changes in form and details may bemade therein without departing from the scope of the inventionencompassed by the appended claims.

1. A method comprising: depositing a biomass material, in particulate form, on a trough of a vibratory conveyor; vibrating the vibratory conveyor and cooling the biomass material, while conveying the biomass material; and exposing the biomass material on the vibratory conveyor to ionizing radiation in the form of at least one electron beam through at least one corresponding opening in the conveyor cover.
 2. The method of claim 1, wherein cooling the biomass material comprises cooling the trough.
 3. The method of claim 1, further comprising comminuting the biomass prior to exposing the biomass to the ionizing radiation.
 4. The method of claim 3, wherein comminuting is selected from the group consisting of shearing, chopping, grinding, hammermilling and combinations thereof.
 5. The method of claim 3, wherein comminuting produces a biomass material with particles, and more than 80% of the particles have at least one dimension that is less than about 0.25 inches.
 6. The method of claim 3, wherein comminuting produces a biomass material with particles, and no more than 5% of the particles are less than 0.03 inches in their greatest dimension.
 7. The method of claim 1, wherein the biomass is irradiated with 10 to 200 Mrad of radiation.
 8. The method of claim 1, wherein the biomass is exposed to more than one dose of radiation utilizing multiple accelerating heads to expose the biomass to a plurality of scanning electron beams while the biomass is being conveyed on the vibratory conveyor, each scanning electron beam being delivered through a corresponding opening in the cover.
 9. The method of claim 1, wherein the biomass material comprises cellulosic or lignocellulosic material.
 10. The method of claim 9, wherein the cellulosic or lignocellulosic material comprises a lignocellulosic material selected from the group consisting of wood, paper, paper products, cotton, grasses, grain residues, bagasse, jute, hemp, flax, bamboo, sisal, abaca, corn cobs, corn stover, coconut hair, algae, seaweed, straw, wheat straw and mixtures thereof.
 11. The method of claim 1, wherein the vibratory conveyor has a covering that includes an opening through which the electron beam is directed.
 12. The method of claim 1, wherein the opening in the cover includes a window foil that allows passage of the ionizing radiation through the window foil and onto the biomass material.
 13. The method of claim 1, wherein the biomass material is conveyed at a rate of at least about 1000 lb/hr.
 14. The method of claim 1, wherein the spreader comprises a drop spreader.
 15. The method of claim 1, wherein the energy of the electron beam is from about 0.3 to 2 MeV.
 16. The method of claim 1, wherein the vibratory conveyor conveys the biomass material at an average speed of from about 3 to 100 ft/min.
 17. The method of claim 1, wherein the material is deposited using a spreader.
 18. The method of claim 17, wherein when it is deposited the biomass material covers only a portion of a width of the trough, and during conveying the biomass material spreads out to cover substantially the entire width of the trough.
 19. The method of claim 1, wherein the electron beam is a scanning electron beam 